The officer, 30, was said to have been shot after arriving at his home in the Phola Village following an urgent call from his 29-year-old wife, according to Mpumalanga News.
The man reportedly died at the scene on Sunday after the bullet hit him beneath his chin, and exited at the back of his neck.
It was stated that the wife then informed her husband’s friend of what she had done, before police were called to the scene.
The woman would appear in the KaBokweni Magistrate’s Court soon, according to police.
This incident follows a KwaZulu-Natal woman facing two counts of murder and one of attempted murder after allegedly killing her husband and mother-in-law during an argument.
The incident had taken place in Mbotsha Ward, Boboyi near Port Shepstone in KZN earlier this month, according to South Coast Herald.
The attempted murder charge stems from an elderly woman, who had been present during the quarrel, sustaining a gunshot wound to the upper arm.
Police said the shooter, who is a police Constable, had handed herself over to the Port Shepstone police shortly after the incident.
Investigations are on-going.