Answer as of 2021:

The best way (actually the only way*) to simulate an actual click event using only CSS (rather than just hovering on an element or making an element active, where you don't have mouseUp) is to use the checkbox hack. It works by attaching a label to an <input type="checkbox"> element via the label's for="" attribute.

This feature has broad browser support (the :checked pseudo-class is IE9+).

Apply the same value to an <input>'s ID attribute and an accompanying <label>'s for="" attribute, and you can tell the browser to re-style the label on click with the :checked pseudo-class, thanks to the fact that clicking a label will check and uncheck the "associated" <input type="checkbox">.

* You can simulate a "selected" event via the :active or :focus pseudo-class in IE7+ (e.g. for a button that's normally 50px wide, you can change its width while active: #btnControl:active { width: 75px; }), but those are not true "click" events. They are "live" the entire time the element is selected (such as by Tabbing with your keyboard), which is a little different from a true click event, which fires an action on - typically - mouseUp.

Basic demo of the checkbox hack (the basic code structure for what you're asking):

label {
    display: block;
    background: lightgrey;
    width: 100px;
    height: 100px;
}

#demo:checked + label {
    background: blue;
    color: white;
}

<input type="checkbox" id="demo"/>
<label for="demo">I'm a square. Click me.</label>

Here I've positioned the label right after the input in my markup. This is so that I can use the adjacent sibling selector (the + key) to select only the label that immediately follows my #demo checkbox. Since the :checked pseudo-class applies to the checkbox, #demo:checked + label will only apply when the checkbox is checked.

Demo for re-sizing an image on click, which is what you're asking:

#btnControl {
    display: none;
}

#btnControl:checked + label > img {
    width: 70px;
    height: 74px;
}

<input type="checkbox" id="btnControl"/>
<label class="btn" for="btnControl"><img src="https://placekitten.com/200/140" id="btnLeft" /></label>

With that being said, there is some bad news. Because a label can only be associated with one form control at a time, that means you can't just drop a button inside the <label></label> tags and call it a day. However, we can use some CSS to make the label look and behave fairly close to how an HTML button looks and behaves.

Demo for imitating a button click effect, above and beyond what you're asking:

#btnControl {
    display: none;
}

.btn {
    width: 60px;
    height: 20px;
    background: silver;
    border-radius: 5px;
    padding: 1px 3px;
    box-shadow: 1px 1px 1px #000;
    display: block;
    text-align: center;
    background-image: linear-gradient(to bottom, #f4f5f5, #dfdddd);
    font-family: arial;
    font-size: 12px;
    line-height:20px;
}

.btn:hover {
    background-image: linear-gradient(to bottom, #c3e3fa, #a5defb);
}


.btn:active {
    margin-left: 1px 1px 0;
    box-shadow: -1px -1px 1px #000;
    outline: 1px solid black;
    background-image: linear-gradient(to top, #f4f5f5, #dfdddd);
}

#btnControl:checked + label {
    width: 70px;
    height: 74px;
    line-height: 74px;
}

<input type="checkbox" id="btnControl"/>
<label class="btn" for="btnControl">Click me!</label>

Most of the CSS in this demo is just for styling the label element. If you don't actually need a button, and any old element will suffice, then you can remove almost all of the styles in this demo, similar to my second demo above.

The closest you'll get is :active:

#btnLeft:active {
    width: 70px;
    height: 74px;
}

However this will only apply the style when the mouse button is held down. The only way to apply a style and keep it applied onclick is to use a bit of JavaScript.

You can use pseudo class :target to mimic on click event, let me give you an example.

#something {
  display: none;
}

#something:target {
  display: block;
}

<a href="#something">Show</a>
<div id="something">Bingo!</div>

Here's how it looks like: http://jsfiddle.net/TYhnb/

One thing to note, this is only limited to hyperlink, so if you need to use on other than hyperlink, such as a button, you might want to hack it a little bit, such as styling a hyperlink to look like a button.

If you give the element a tabindex then you can use the :focus pseudo class to simulate a click.

HTML

<img id="btnLeft" tabindex="0" src="http://placehold.it/250x100" />

CSS

#btnLeft:focus{
    width:70px;
    height:74px;
}

http://jsfiddle.net/NaTj5/

Edit: Answered before OP clarified what he wanted. The following is for an onclick similar to javascripts onclick, not the :active pseudo class.

This can only be achieved with either Javascript or the Checkbox Hack

The checkbox hack essentially gets you to click on a label, that "checks" a checkbox, allowing you to style the label as you wish.

The demo