Skype is an excellent service for VoIP and is very widely used. Currently using iPhone Skype application, you can make phone calls using Wifi, but very soon you will be able to make phone calls using the 3G network which was recently announced.
Check out this Video
Right now there are some other good applications like TruPhone which I use works with the 3G network already.
There was a restricting the iPhone SDK on making phone calls using the 3G earlier, but with the release of version 3.2, this was removed and opened up the option to use 3G for phone calls.
Now we see companies and developers showing more interest with the launch of iPad.
I wish if iPhone opens up support to multitasking or at least have an option to run a few programs in the background, which is the only thing that I am missing in my iPhone 3G S
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Skype will appear on iPad when iPad launch