This tip was found by “my favorite”, Chris_Ace2

With version 4.0, Skype has added a new switch for supporting multiple users on a single PC. The following steps would show how to create a new shortcut for starting a new Skype instance with a different Skype user account.

Open Windows Explorer and go to “C:\Program Files\Skype\Phone.”

Right click on the Skype icon and select “Create Shortcut.”

Right click on the new shortcut and select “Properties.”

Append ” /secondary” to “Target” to become ‘”C:\Program Files\Skype\Phone\Skype.exe” /secondary.’

Click OK to save the change.

Give the new shortcut a new name and move it to anywhere you desired.

When you click on this new shortcut, a new Skype window will appear and you can log on using another Skype account.

You can also run the new Skype instance under another Windows user account. Right-click on the new icon while holding down the shift key, then select “Run as.” See below for more details.

Setting up multiple Skype account on a PC

You have a Skype account on your computer, but so does your wife / husband, and so does your kids? None of you want to miss your important Skype calls from your friends. There is no need to fight over who should / shouldn’t be logged-in on your only computer at home. So here is the way around the brewing storm:

Build up a new user account in Windows XP:

1. Start -> Control Panel -> User Accounts -> Create a new account (Under Pick a task.)

2. Key-in your new account name in the “type a name for the new account:” box -> Next

3. Click Computer Administrator -> Create Account

Give the account you just created a password:

1. Start -> Control Panel -> User Accounts -> Left-click on the new account you just created.

2. Left-click on Create a password -> Enter the password two times and enter the password hint -> Create Password

Run the second Skype program using the new account you just set up:

1. Right-click on the Skype Icon on your desktop while holding down the shift key -> Left-click on Run as

2. Click The following user -> Choose User name and enter password / OK

Click on the New Users – Create a Skype Account tab if you need to register a new user in Skype, and follow the instructions on screen.

Click on the Existing Users – Log in to Skype tab if you already have a second account, and follow the instructions on screen.

Update 10/09/2008: We have created the following Youtube Video Clip for you, just in case you want somebody to show the steps in action. Have Fun.

via How to Log-in Multiple Users in SKYPE on a WIN XP Machine.