I have found that it is possible to run multiple instances of Skype using the /secondary key.

The second instance, however, asks to enter or select credentials, while I want it just to pick the username which have not been used by the first instance.

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The only solution I have found and use is combining the /secondary key with the /username: key:

start /D "C:\Program Files (x86)\Skype\Phone" Skype.exe /username:user1 /secondary
start /D "C:\Program Files (x86)\Skype\Phone" Skype.exe /username:user2 /secondary

This requres pressing a button Sign me in in the second instance's welcome window. This fills in the passord automatically, however.

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