It is great that Skype allows us to login with multiple Skype account in same computer.You only need to open another Skype window by below process.
Press Window key + R
Windows key + R
A Run box will open. Enter “C:\Program Files\Skype\Phone\Skype.exe” /secondary in that box, if you have 32 bit operating system and command syntax for 64 bit is “C:\Program Files (x86)\Skype\Phone\Skype.exe” /secondary.
Hit enter or click on Ok.
Above syntax use default path of Skype. If you have installed Skype in different location use that path for skype.exe.
If you get error message. Try below solution.
Search skype file in C:\Program Files\Skype\Phone\ for 32 bit operating system and for 64 bit search file in C:\Program Files (x86)\Skype\Phone\.
Create shortcut of skype.exe file on desktop. Now got to the shortcut, right click and open the Properties.
Enter “C:\Program Files\Skype\Phone\Skype.exe” /secondary in Start in path and click ok.
Now this is the shortcut for your new account, whenever you will double-click the icon, a new Skype window will open.
Techno Crowd 