No reason has been given for the departure of Webb, who does not have a new job lined up, and it is understood that the terms of his severance prevent him from discussing the issue.
This follows the ousting of NGN marketing director Belinda Furneaux-Harris a year ago following a dispute over marketing strategy.
Webb joined NGN from Optimedia a decade ago. He was instrumental in the creation of the Newspaper Marketing Agency, and oversaw the operations of The Sun and The News of the World.
He reported to managing director Camilla Rhodes, who joined NGN in November 2001 in a job swap with her husband, Clive Milner.
Milner took on his wife's former role of managing director at TNL, before being promoted to group managing director at News International. He now takes on additional responsibilities for IT and Times supplements.
TNL is seeking a replacement for Mullins, who was recently listed at number 42 in Marketing's Power 100.
In other moves, TNL commercial director Mike Gordon will take over Webb's role at NGN, while Paul Hayes has been promoted from general manager to managing director of TNL.
Ian Clark has moved from NGN, where he was commercial director, to join TNL as advertising director. Trading, revenue development and online activities are consolidated under his remit.
Mathew Watkins and David Emin retain their sales director roles at TNL and NGN respectively.
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