The Polish coach – who first coached Mali between 2001 and 2002 – returns to the country ahead of qualification for the 2015 Africa Cup of Nations in Morocco.
Mali will take on South Africa, Nigeria and Mozambique in Group A of the competition and will be hoping to repeat their efforts at the 2002 tournament, when Kasperczak led them to fourth place.
The 67-year-old coach takes over from Patrice Carteron, who resigned earlier this year, and is excited to start his new role.
"I am very pleased and proud to come back to Mali," Kasperczak said. "I have great memories over there. I had an amazing time in 2002."
Kasperczak has a wealth of experience within African football, having previously coached Ivory Coast, Tunisia, Morocco and Senegal.
His time with Senegal was the most recent of those spells, leading the country from 2006 to 2008.
