Expand div from the middle instead of just top and left using CSS

The key is to transition the margin by a formula. There is a little "wiggle" that is annoying during the transition if it is floated.

EDITED ADDING OPTIONS

Option 1: Expands within space reserved around it http://jsfiddle.net/xcWge/14/:

#square {
    width: 10px;
    height: 10px;
    margin: 100px; /*for centering purposes*/
    -webkit-transition: width 1s, height 1s, margin 1s;
    -moz-transition: width 1s, height 1s, margin 1s;
    -ms-transition: width 1s, height 1s, margin 1s;
    transition: width 1s, height 1s, margin 1s;
}
#square:hover {
    width: 100px;
    height: 100px;
    margin: 55px; /* initial margin - (width change (and/or height change)/2), so here 100px is initial margin, and the change is (100px final W/H - 10px initial W/H = 90px change, so 100px - (90px / 2 [= 45px]) = 55px) */
}

Option 2: Expands over elements around it http://jsfiddle.net/xcWge/18/:

#square {
    width: 10px;
    height: 10px;
    margin: 0; /*for centering purposes*/
    -webkit-transition: width 1s, height 1s, margin 1s;
    -moz-transition: width 1s, height 1s, margin 1s;
    -ms-transition: width 1s, height 1s, margin 1s;
    transition: width 1s, height 1s, margin 1s;
}
#square:hover {
    width: 110px;
    height: 110px;
    margin: -50px; /* 0 - (110px - 10px [= 100px]) / 2 =  -50px */
}

Option 3: Expands over elements before it in flow and shifts elements after it http://jsfiddle.net/xcWge/22/:

#square {
    width: 10px;
    height: 10px;
    margin: 0;
    position: relative;
    top: 0;
    left: 0;
    -webkit-transition: width 1s, height 1s, top 1s, left 1s, margin 1s;
    -moz-transition: width 1s, height 1s, top 1s, left 1s, margin 1s;
    -ms-transition: width 1s, height 1s, top 1s, left 1s, margin 1s ;
    transition: width 1s, height 1s, top 1s, left 1s, margin 1s;
}
#square:hover {
    width: 110px;
    height: 110px;
    top: -50px; /* initial top[0] - (new height[110px] - initial height[10px] [=100px])/2 [=50px] = -50px) */
    left: -50px; /* initial left[0] - (new width[110px] - initial width[10px] [=100px])/2 [=50px] = -50px) */
    margin-right: -50px;
    margin-bottom: -50px;
}

ADDED NON-SQUARE EXAMPLE

A comment was made this does not work for a non-square (same width/height), but that just means one has to adjust differently for each direction during the transition. So here is Option 2 (with non-square) that starts as a rectangle, and the width expands twice as much as the height (so changes rectangle shape even) during the transition: Expands over elements around it http://jsfiddle.net/xcWge/2131/

#rectangle {
    width: 110px;
    height: 10px;
    margin: 0; /*for centering purposes*/
    -webkit-transition: width 1s, height 1s, margin 1s;
    -moz-transition: width 1s, height 1s, margin 1s;
    -ms-transition: width 1s, height 1s, margin 1s;
    transition: width 1s, height 1s, margin 1s;
}
#rectangle:hover {
    width: 310px;
    height: 110px;
    margin: -50px -100px; /* initial margin - ((initial margin - width change (or height change))/2) */
}

If the width were only changing by 100px also (so from 110px to 210px), then just a margin: -50px would have still worked.

You'll have to transition it's position in order to do this as well, setting it to relative/absolute and changing the top value as it animates.

(edit based on comment)

Instead of absolute positioning, you could try to do the same sort of thing with a negative top margin. That would keep it in the document flow. Somehow, though, you need to actually move the div as well as animating the height/width.

you may have to make you're div position absolute and then adjust the left and top position on hover. jsFiddle example