In a joint statement, the TUC and London 2012 organisers said working on the Games would be one of the most "memorable" life and work experiences for the employees.
Lord Sebastian Coe, chairman of the London 2012 Organising Committee, said: "These principles identify the foundations for a smooth and stable industrial relations environment at the broadest level, with all parties working together to the same objective - the successful delivery of the Olympic Games and Paralympic Games in 2012.
"We want to deliver a memorable Games and a great experience for everyone - including our workforce - and very much welcome the TUC's support."
TUC general secretary Brendan Barber said: "Today's agreement will help to ensure that London 2012 will be a fantastic experience for those building and running the Games, as well as for those watching and participating in it."
The so-called Principles of Co-operation included ensuring a safe working environment, with effective industrial relations and fair terms and conditions of employment.