"Depending on the topic that we agree on, I think he can use his voice to help us in some of the work that we do, just as people like Michael Douglas have been very active in disarmament," he said.
Pierce Brosnan, the Irish-born actor who plays James Bond, has had a series of briefings at UN headquarters in New York to explore what he can do for the world body.
As James Bond, Pierce Brosnan has a licence to kill - but in real life, the actor wants a licence to protect the environment, to help children in crisis and to eliminate nuclear weapons.
007 usually spends his time battling to save the world from international criminals, but Kofi Annan believes that in between films he can be another high-profile representative for the UN.
"Depending on the topic that we agree on, I think he can use his voice to help us in some of the work that we do, just as people like Michael Douglas have been very active in disarmament," he said.
"I think celebrities can be very effective advocates provided the issue is right."
Star-studded cast
The UN already employs a host of goodwill ambassadors to promote its causes.
One is the former James Bond actor, Roger Moore.
Former heavyweight boxing champion Muhammed Ali, actors Mia Farrow and Peter Ustinov, and supermodel Claudia Schiffer are also in the celebrity line-up.
A spokesman for Pierce Brosnan said the actor had been inspired by his briefings at the UN, but would not be talking in detail about the organisation's work until he decides exactly which cause he wants to adopt.