Open your xfire_games.ini which you'll easy find with "Search".
Find The Elder Scrolls: Skyrim paragraph.
And replace it with this:
[6984_1]
LongName=The Elder Scrolls V: Skyrim
ShortName=skyrim
LauncherDirKey=HKEY_LOCAL_MACHINE\SOFTWARE\The Elder Scrolls V Skyrim\InstallPath
LauncherExe=SteamApps\*\skyrim\TESV.exe
DetectExe=SteamApps\*\skyrim\TESV.exe
Launch=%UA_LAUNCHER_EXE_PATH% %UA_LAUNCHER_EXTRA_ARGS% %UA_LAUNCHER_NETWORK_ARGS%
InGameRenderer=D3D9
InGameFlags=ENABLE_MOUSE|USE_DINPUT_MOUSE
[6984_2]
LongName=The Elder Scrolls V: Skyrim
ShortName=skyrim
LauncherDirKey=HKEY_LOCAL_MACHINE\SOFTWARE\The Elder Scrolls V Skyrim\InstallPath
LauncherExe=The Elder Scrolls V Skyrim\TESV.exe
DetectExe=The Elder Scrolls V Skyrim\TESV.exe
Launch=%UA_LAUNCHER_EXE_PATH% %UA_LAUNCHER_EXTRA_ARGS% %UA_LAUNCHER_NETWORK_ARGS%
InGameRenderer=D3D9
InGameFlags=ENABLE_MOUSE|USE_DINPUT_MOUSE
Xfire, should work in-game now.
Cheers!
