From the Skype support website the steps for running two instances of Skype at the same time on Windows are:
- Click the Start button > Run (or press the Windows and R keys on your keyboard at the same time)
- In the Run window for 32-bit operating systems type: “C:\Program Files\Skype\Phone\Skype.exe” /secondary
- In the Run window for 64-bit operating systems type: “C:\Program Files (x86)\Skype\Phone\Skype.exe” /secondary
- 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.
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