The Malmesbury Stock Theft Unit teamed up with Crime Intelligence and Cape Nature Reserve to conduct a clandestine operation over the weekend in Citrusdal in the Western Cape.
Spokesperson Colonel Andre Traut says this led to the arrest of four suspects who were found in possession of rhino horn and protected flora.
He says the value of the confiscated items is yet to be determined.
The men aged 23, 30, 36 and 46 are expected to appear in the Citrusdal court on Tuesday.
More poachers were arrested in two similar operations earlier this month.
In these arrests, Cape Nature together with SAPS confiscated 11 000 endangered succulent plants destined for the illegal plant trade.
The arrests were made on the 30th of April and the 8th of May in the Matzikama region of the province.