Actually a little more info would be helpful. But let's just take what we have. You've used AMD overdrive, which is good for AMD overclocking, its a helpful tool.
I believe, although I could be wrong, that overdrive saves your profile and it launches a program when windows starts called AOD helper. I believe its the job of this "helper" to save the profile and create the settings, even though Overdrive is not running. Thus when in bios, you are seeing what is set by the bios. However when you boot to windows, AOD pushes the new settings. I think that accounts for the difference in voltage readings you are experiencing.
Thats what AKM800 was saying, that most overclockers prefer to bios overclock as this will be more stable in windows than software. Conflicting information from the bios and windows software will not give the best results.
Here's an article on AMD overclocking:
http://www.tomshardware.com/reviews/phenom-overclock-athlon,2161.html
As the article suggests, AMD overdrive is a good place to start, as it is helpful in determining the max multi, max front side bus, and other settings instead of changing a setting in bios, booting back to windows, and leaving windows again to change bios.
Once you have a good idea of where you need to be from your AOD settings, then reboot to bios to fine tune and set everything accordingly.
As for the AOD helper, I simply disabled it from startup via msconfig, as it never really worked properly for me anyway!
😉