Matsatsantsa are scheduled to face Amakhosi in the 2018 Telkom Knockout quarter-final match at the Moses Mabhida Stadium in Durban on Sunday.
Tembo made it clear that they cannot afford to underestimate Chiefs, who have failed to win their last four matches in all competitions (in regulation time).
“Chiefs are the favourites," Tembo was quoted as saying by Daily Sun.
Amakhosi are wounded as they are coming off a 2-1 defeat to their arch-rival Orlando Pirates in a titanic PSL match in Johannesburg last weekend.
Tembo, who was appointed permanent SuperSport head coach prior to the start of the current season, feels that Chiefs have the potential to cause us big damage.
"We won’t underestimate them because they have the potential to cause us big damage," the retired defender continued.
SuperSport are undefeated in their last four matches in all competitions, but they are also winless in their last five games (in regulation time).
The three-time Premier Soccer League (PSL) champions will be hoping to return to winning ways against the Glamour Boys.
"It would be foolish to think we can go to them and beat them just because they are experiencing a bad run," the former Zimbabwe international concluded.
This will be the third meeting between SuperSport and fellow South African cup kings Chiefs, this season.
Tembo masterminded a win over Chiefs on aggregate in the two-legged 2018 MTN8 semi-final tie, and SuperSport advanced to the final where they lost to Cape Town City.
A 2-2 draw at the Lucas Moripe Stadium in Tshwane in the first-leg clash was followed by a 1-0 win over Chiefs at the FNB Stadium in Johannesburg.