More than 100 business and government leaders will hit streets around Australia to sell copies of The Big Issue and help shine a spotlight on the magazine's homeless and disadvantaged vendors, who are working to improve their lives.

The leaders will don the fluoro vest and sell the magazine in 30-minute sessions at various times and locations during the week.

In Australia, more than 6500 men and women have earned an income through selling The Big Issue in the past 20 years. Vendors buy copies of the magazine for $3.50 and sell them for $7, keeping the difference.

Among those joining in is Greens MLA and multi-portfolio minister Shane Rattenbury, who sold The Big Issue outside the Canberra Centre with vendor Tau on Wednesday.

Tau, who has cerebral palsy, started selling The Big Issue in 2009. The massive Brumbies fan says selling the magazine has made him feel independent and "a useful member of the community".

It was the third time Rattenbury had volunteered to sell the magazine.

"For me, the thing with The Big Issue is that it's providing a job for the sellers. They're not begging, they're selling a product which is a good and interesting read," he said.

"There is sense of worth for the vendors and a sense of achievement from selling it."

While Canberrans were generous, Rattenbury still took his hat off to the vendors.

"It's a tough gig for the vendors. They're out in all sorts of weather, in all sorts of spots, and lots of people don't stop," he said.

But there were plenty who did. And they built up a relationship with the vendors like Tau.

"Lots of people were stopping to say hello," Rattenbury said. "It was great to see that connection and community spirit."