About 150 former soldiers belonging to a nationalist group led by major Antauro Humala seized the station in the Andean town of Andahuaylas, taking 11 officers hostage.
The rebels then blocked the roads in the city and demanded President Alejandro Toledo's resignation.
Andahuaylas has a population of 30,000 and is located about 400km southeast of the capital, Lima.
On Sunday, four police officers were killed when 300 heavily armed police attempted to storm rebel positions in the city.
But despite successfully resisting the police raid, Humala said his followers would surrender at noon (1700 GMT) on Monday in the town square "in presence of the people".
He promised his forces would not open fire until then, "but only if the other side does not harass or shoot at us".
The announcement came after Prime Minister Carlos Ferrero demanded that the group surrender and promised that their lives would be spared.
Peruvian President Toledo
has low popularity ratings
Toledo, who has a nationwide approval rating of about 11%, declared a regional state of emergency and said the government would act with "a firm hand" to quell the revolt.
"Those who have seized government buildings, who have killed and taken hostages - this my government will not permit," Toledo said on Sunday after visiting police wounded in an assault on the rebels' positions.
It was not the first time Peruvians had heard from Humala.
His brother, Ollanta Humala, led a month-long military uprising in October 2000 against the government of Alberto Fujimori, who resigned in November 2000 amid a corruption scandal.
The Humala brothers were briefly imprisoned, but pardoned after Fujimori left office. They were allowed to stay in the army.
Antauro Humala had originally said his brother was en route to Peru to lead the uprising, but on Sunday Ollanta urged the rebels to negotiate with the government.
The rebels belong to the Etnocacerista Movement, a reference to Andres Avelino Caceres, a hero of the 1879-1883 War of the Pacific who led a campaign of resistance against the Chilean occupation.
Most of the former soldiers are veterans of the 1995 war with Ecuador and the war with the Shining Path Maoist rebels in the 1980s and 1990s. They are calling for the resignation of Toledo, saying he is a corrupt sellout to foreign investors.