London 2012 needs to sign up 70,000 volunteers in what is being described as the biggest recruitment exercise since the Second World War.
''Volunteers are hugely important and it is one of the big things I remember about Vancouver,'' said Williams, the women's skeleton champion from this year's Winter Olympics.
At the Winter Games in Canada in February the whole country seemed to be gripped by a sense of achievement – and there is no reason why Britain should not feel the same, according to Williams, 27.
She said: ''London 2012 is basically an amazing opportunity for our athletes to compete in their own country and I think, judging from my experience in Vancouver, it was an amazing experience for the Canadians in Canada.
''It was something for the whole nation and it will be the same here with the bubble of excitement growing.
''It is a proud moment for a country to have the Olympics in their own country and to know as an athlete that we are part of it.
''Obviously there are only so many people who can compete and be competitive but what a good way to help with the experience and to be part of it.''
Hopefuls must be at least 18 on January 1, 2012, available to volunteer for at least 10 days during either the Olympic Games or the Paralympic Games and at least three days of training before the events.
There will be no free tickets for the 2012 competitions.
