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To use more than one Skype account on the same computer at the same time, you need to start a new instance of Skype.
For 32-bit operating systems:
"C:\Program Files\Skype\Phone\Skype.exe" /secondary
For 64-bit operating systems:
"C:\Program Files (x86)\Skype\Phone\Skype.exe" /secondary
If you get an error message, copy and paste the exact command from this page and try again.
Be aware that if you’ve changed the installation path for Skype, then you’ll need to enter the correct path for the Skype.exe file.
If the above solution fails, you can try another option:
If you’re running 64-bit operating system, you can find the file in C:\Program Files (x86)\Skype\Phone\.