When you plug in several USB devices at the same (especially a portable hard drive) there often isn't enough "juice" available via USB to power them all because power at each port is limited and fixed, as is the total amount of power for all the ports added together.
You'll know when you've reached the limit because a device will keep triggering the connected and disconnected sound without you even touching it..
A powered hub solves that problem, but of course it will work without mains power too provided the USB ports can satisfy the power demands on their own.
Even where sufficient juice through USB isn't an issue, a hub gives you the convenience of more USB ports, but it still pays to get a mains powered hub rather than one without a mains adapter 'cos you never know when you might come up against that power issue.