Now the 52-year-old wife of President Mugabe is accused of beating model Gabriella Engels, 20, on Sunday evening at the Johannesburg hotel where her two sons were staying.
Police minister Fikile Mbalula put the order in place on Thursday.
This while the Zimbabwean government has made representation to the International Relations Department for diplomatic immunity in the case against Mugabe.
At a press conference, well-known prosecutor Gerrie Nel, who secured the conviction of disgraced Paralympian Oscar Pistorius, announced that he would be representing Engels in the case against Mugabe.
The police said the Zimbabwean government asked for diplomatic immunity for a suspect involved in the alleged assault.
Zimbabwe's state-owned Herald newspaper reported last weekend that she was in South Africa seeking medical care.
Earlier, South African police had been negotiating with Grace's lawyers to get her to turn herself in to face charges of assault in a court room, a senior police source said.
It came after Ms Engels posted a photo of a deep gash to her forehead which she said was inflicted by Mrs Mugabe as her bodyguards looked on.
Dictator Robert Mugabe, left, pictured with his wife, right, is also in South Africa in response to the assault allegations.
Engels and her mother were present at the media briefing.
But‚ he said‚ in order for diplomatic immunity to apply‚ she should have applied before she entered South Africa.
Nel said he was impressed that the family did not want a civil lawsuit.
Spies said they will approach the court if Mugabe is granted immunity‚ because they believe her claim she was accompanying her husband Robert to a SADC summit in South Africa was an "afterthought".
Nel also revealed that they would be "monitoring the procedure every step of the way" and if all else fails they will take the private prosecution route.
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"We were expecting a statement from her", he said, according to the domestic ANA news agency.