The appointments come as Wembley, a subsidiary of the Football Association, seeks to bring in millions of pounds in sponsorship revenue by signing up founding sponsors for the stadium, which opens in 2006.
Gregory and Frayling,marketing and communications director and head of commercial and PRs respectively, will sign at least four sponsors and develop revenue streams for the stadium.
Gregory is a former sponsorship manager at Walkers Crisps, and will report to Jonathan Hill, group commercial director for both the FA and Wembley, and Wembley chief executive Michael Cunnah.
Frayling, who was responsible for the Carling Live music sponsorship programme, will report to Gregory. He will work with head of sponsorship Clive Richards and head of marketing Jane Baker. Frayling will be responsible for managing and developing the stadium's event calendar and will drive income by booking music acts. The stadium already has the rights to hold six major music events.