The Romanian stepped down from his post just five months into his tenure, citing "personal reasons."
He was in charge of just seven games, including two defeats and a draw at the 2025 Africa Cup of Nations that saw the Warriors finish bottom of Group B.
The Sekhukhune development coach and Zimbabwe assistant Tembo will now step into the post on an interim basis.
A Zimbabwe Football Association statement read: "The Zimbabwe Football Association [ZIFA] announces that Mario Marinica has resigned from his position as head coach of the Zimbabwe senior men’s national team, citing personal reasons.
"ZIFA has accepted his resignation and thanks Coach Marinica for his contribution to the Warriors. The Association wishes him well in his future endeavours."
Zimbabwe are next in action at the Unity Cup in May, featuring Nigeria, Jamaica and India.
"Kaitano Tembo has been appointed Interim head coach and will lead the team for the upcoming Unity Cup assignment in the United Kingdom. He will be assisted by Takesure Chiragwi, who has been appointed assistant coach," continued the statement.
The Proteas Women will travel to Bulawayo in September for a historic first-ever T20 International series against Zimbabwe Women, with the neighbouring nations set to contest five matches at Queens Sports Club.
Kaitano Tembo says he is proud to lead Zimbabwe at the upcoming Unity Cup to be held at the Valley Stadium in London.
Belgian giants Anderlecht have reportedly renewed their interest in Zimbabwe international Tawanda Maswanhise following his impressive season with Motherwell.
Zimbabwe midfielder Marshall Munetsi says the Warriors are eager to measure themselves against the Super Eagles ahead of their highly anticipated Unity Cup clash next week Tuesday, 26 May.
