How to remove outdated offline files path / links from Windows workstation...

Open registry editor (Start-->Run--> REGEDIT command) on affected machine and navigate to

\HKEY_CURRENT_USER\Software\Microsoft\Windows\CurrentVersion\NetCache\Shares

Remove all outdated sub-folders under Shares...

 Now perform offline files database reinitialization by adding following registry entry:

Windows XP

HKEY_LOCAL_MACHINE\SOFTWARE\Microsoft\Windows\CurrentVersion\NetCache

Key Name: FormatDatabase
Key Type: DWORD
Key Value: 1
  
Windows 7

HKEY_LOCAL_MACHINE\SYSTEM\CurrentControlSet\Services\Csc\Parameters 

 Key Name: FormatDatabase
Key Type: DWORD
Key Value: 1

Keep in mind that all your offline file cache will be removed upon reboot - make sure all your unsynced files are backed up!

Reboot the computer and wait for database to reinitialize (depending on your offline files cache size this could take some time)... Upon completion of reinitialization FormatDatabase registry key will be removed automatically.

Additional info:

How to reset Offline Files cache database on XP (old server synchronization links) below:
http://www.searchmarked.com/windows/how-to-reset-the-offline-folder-cache-on-windows-xp.php

How to re-initialize the offline files cache and database (Microsoft article) below:
http://support.microsoft.com/kb/230738