Just recently Skype announced the availability of making video calls on the new Skype 2.0 version but only for a few devices like Nexus S and Xperia Neo and Pro. Now, thanks to a user at XDA developers, we can have the same features on many devices, included Samsung Galaxy S ( Captivate in my case).
I tasted today and really works. You have to option of switch cameras from front to back.
If you guys want to try it here is the link (download here)
Another pic after the jump