Tembe, who has nearly 20 years of experience with emergency management services, took over his new position on Tuesday after Johannesburg Mayor Herman Mashaba announced his appointment.
Mashaba said Tembe holds a National Diploma in personnel management, metro policing, as well as FBI law enforcement executive leadership (Virginia, USA).
He has also attended seminars on law enforcement leadership in the USA since 2009, he said.
However, the ANC accused the Democratic Alliance-led coalition in Johannesburg of flouting appointment processes.
"The Democratic Alliance-led coalition in the City of Johannesburg has once again demonstrated that they are prepared to flout recruitment and appointment processes to appoint the candidates they want, despite those candidates failing dismally in the interview process," said ANC regional spokesperson Jolidee Matongo.
Matongo said that Tembe's appointment was proof of that.
In a statement, Matongo said, at the 5th Extraordinary Council Meeting held onOctober 19, last year, Mashaba had brought a report to appoint General Eric Gela as the chief of police for the city.
"In that same report, David Tembe was scored as candidate number five. After discussions at this meeting the mayor withdrew the report and the matter was sent back to the executive for further consideration," he said.
There were no further interviews for the position after the meeting, he claimed.
"Instead, a new report on the appointment of the chief of police was presented to council on November 29, 2017.
In this new report, David Tembe was recommended for appointment as the chief of police."
He said the ANC caucus rejected this appointment as it did not afford the highest-scoring candidates the opportunity to be appointed to the position.
He said one of the recommendations made by the recruitment panel suggested that the reason for recommending the fifth candidate (Tembe) was that this was a crucial position and the city preferred a candidate who would be able to take up the position immediately.
"The advantage of this candidate is that he meets the requirement of being a registered member of the municipal police service. The first four candidates are unfortunately not registered members of a municipal police service and the process of ensuring the necessary training and registration, would take months to conclude," the recommendation read.
He said this recommendation, "if it indeed came from the panel," clearly demonstrated that David Tembe was not the most suitable candidate to be appointed.
"Therefore, his appointment will be challenged by the ANC, using all available avenues. We will in the meantime approach the MEC for Cooperative Governance in the province and the Minister of Public Service and Administration to look into the matter."
He said the ANC has also given its legal team all the required documentation to start a process to have Tembe's appointment set aside.
JMPD spokesperson Chief Superintendent Wayne Minnaar could not comment on the matter.
"I can't give a comment because the appointment of the chief is administrative, you'll have to call the mayor's office for that," he said.
Mashaba said on Tuesday: "I have every confidence in Mr Tembe's abilities and look forward to working with him as we run a corruption-free city that respects the rule of law and stimulates economic growth for our people.
"I would like to express my deepest appreciation to JMPD's leadership team for providing the necessary support during the past transition period," he said.