A policeman and another soldier were wounded in the attack close to midnight in Barangay Bulo in Matnog town.
Killed were Matnog police chief Senior Inspector Eduardo Amande, Jr., Pfc. Alex Cortez and militiaman Roger de Leon.
Wounded were Pfc. Saldy de la Cerna and Police Officer 2 Reynaldo Garcera.
De la Cerna was rushed to the Sorsogon City Provincial Hospital, while Garcera was treated at the Matnog District Hospital.
Amandes body was brought to Matnog police station, while those of Cortez and De Leon were taken to funeral parlor in Sorsogon City.
Sorsogon police director Senior Superintendent Arnold Revilla said Amande organized a posse of police and soldiers to check the reported presence of NPA rebels in Barangay Bulo in Matnog when NPA rebels, hiding near a school building, opened fire on them.
"The rebels were already positioned near the elementary school building and on the opposite side of the road at the barangay," he said.
Some of the police and soldiers managed to fire back, but it was not immediately clear if there were casualties among the undetermined number of rebels, he added.
Lt. Col. Ernesto Pascual, Army 21st Infantry Battalion commander based in Barangay Aniog in Juban town, Sorsogon, immediately dispatched two platoons of troops to track down the NPA rebels.
"The NPA rebels are trying to show they have not been weakened with the capture of the top commander of Guerrilla Front 79 in Sorsogon last year, as well as top cadres of the Bicol Regional Party Committee," he said.
Revilla said this is the second encounter between the NPA and Sorsogon policemen.
Last Dec. 11, Amande figured in a firefight with about 20 NPA rebels resulting in the killing of an NPA guerrilla as well as two civilians who were caught in the crossfire.
The encounter also left a policeman wounded, including four children.
The wounded NPA rebel, Amado Gabad of Juban, Sorsogon, showed a sketch of the town proper indicating the location of the police station.
The police also recovered a caliber .45 pistol, a 9-mm. Beretta handgun and various ammunition and two cellular phones during that encounter.
In Mindanao, three suspected NPA gunmen shot dead a barangay chairwoman in Talisayan town on Sunday, provincial police chief Superintendent Lyndel Desquitado said.
She was killed after trying to ensure that the rebels would not infiltrate her town, local residents said.
The military has stepped up counterinsurgency operations in Sorsogon in recent months.
NPA rebels are on a list of terrorist organizations and have vowed to escalate attacks this year, hoping to bring about the downfall of President Arroyo. Celso Amo, Cet Dematera, Cecille Suerte Felipe, AFP