The former Bafana Bafana star last month linked up with the Durban-based outfit, who are seeking an immediate return to the topflight following their relegation last season.
Steve Barker's side are seventh on the National First Division table with 33 points from 21 games - 10 points adrift of pace-setting Baroka FC.
“It’s a great honour to be assistant coach alongside Steve Barker,” Buckley told the club’s official website.
“I have wanted to be with AmaZulu for a long time. I tried in 2012 but it didn’t happen and that’s why I went to play at Maritzburg United instead.
“I tried again in 2013 and the deal didn’t work out. But things happen in threes sometimes. I applied for the assistant coach job and things happened this time.
“I hope to help AmaZulu get promotion back into the PSL topflight because I believe it is a team and club that belongs in the PSL.”
The 38-year-old, who was released by Maritzburg United in May 2014, spent most of his playing career at German teams VFL Bochum, Arminia Bielefeld and Borussia Dortmund, while he earned 73 international caps.