You may want to run multiple Skype accounts at the same time if there's one you use just for work, and another one for friends and family. While it’s not possible to run more than one instance of Skype on the same device at the same time, there are still a few ways you can access more than one account at a time:
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Use multiple devices : Sign into your work account on your PC, and your personal account on your phone for example.
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Use Skype for Web : You just need a supported browser and working internet connection, and you can be signed into Skype for web at the same time you're using your desktop or mobile version.