The incident the second double shooting of policemen in two days.
Militants on Monday shot dead two Pakistani officers, the second double shooting of policemen in two days, police said.
The two police brothers Taseer Khan, 30, and Derwaish Khan, 43, were ambushed as they were driving to work on a motorcycle in the Charsadda district of northwestern Khyber Pakhtunkhwa province, police said, adding they died instantly and the attackers fled the scene after the ambush.
"They had no personal enmity. Both brothers were in uniform and were coming on duty. They died on the spot," Nisar Khan Marwat, Charsadda district police chief, told AFP.
Gunmen similarly killed two policemen on Saturday in Hayatabad, on the outskirts of Peshawar and next to Khyber district, part of Pakistan's lawless tribal belt, which lies on the Afghan border.
Pakistani intelligence officials blamed the attack on the Taliban.