The 29-year-old frontman is currently a free-agent after parting ways with Chiefs when his contract expired at the end of June, 2017.
Stars general manager Rantsi Mokoena has revealed that Mthembu is expected in Bethlehem on Wednesday ahead of his proposed move to the club.
The well-traveled player and Ea Lla Koto are set to continue negotiations expected to be concluded by the weekend.
“We have been talking to him over the past few days and we are expecting him to arrive here Bethlehem anytime on Wednesday afternoon‚" Mokoena told Sowetan Live.
"We are hopeful that negotiations will go smoothly and a deal concluded as early as next week," he concluded.
Last January, Chiefs gave Stars' provincial rivals Bloemfontein Celtic permission to assess Mthembu with a view to signing him.
However,Mthembu failed to impress the Siwelele technical team and he returned to Amakhosi.
The forward netted once in 27 PSL appearances during his three-year stint with Chiefs.