Brigadier Hangwani Mulaudzi said the men, aged 35 and 31, stole the horn from their employer's cabinet while he was on holiday and tried to sell it to an undercover police officer.
"The 'covert' buyer requested to see the merchandise and once satisfied, they agreed on a R200 000 payment."
The men were unknowingly led to a police station where the exchange was supposed to happen.
They were arrested and are expected to appear in the Lephalale Magistrate's Court on Wednesday on charges of theft and possession of a rhino horn.
Their employer had confirmed to the police that a rhino horn licensed under his name was stolen from him nearly two weeks ago.
"He had gotten it from one of his rhinos that died in 2011," said Mulaudzi.