Can Xbox One S and DualShock 4 controllers work over bluetooth at the same time?

You should be able to pair all of them to the same PC with one Bluetooth dongle. I just tested with two Xbox One S controllers and two Dualshock 4 controllers and it worked fine. You may need third party drivers for the Dualshock 4 depending on the software you're trying to use it with.

Don't buy the official dongles. The Xbox One dongle is only for the OLD pre-S gamepads that do not support Bluetooth. The dongle does nothing for Xbox One S controllers. The Dualshock 4 dongle will work but it can only handle one controller at a time and isn't necessary if you already have a working Bluetooth dongle.

Both controllers work well with a micro USB cable.