I tried sitting on a ball at home some time ago, but after a couple of hours on it, my back is on fire. It did not go away after about a week of trying, so I gave up.
It's also important to get a ball of the right size (they typically are available in 10cm increments, with 55-75cm being the more common sizes). Look for charts online for sizing info, and then make sure it is inflated enough that when you're sitting on it the angle of your knees is 90 degrees.
While this change has helped my posture, increased my core strength and more, I think my next change is going to be for a treadmill desk so that I can increase the number of calories I burn throughout the day.