Gul Wali Khan, deputy commander Frontier Reserve Police, was critically injured as he received multiple bullet wounds, police said.
He was rushed to the city's Lady Reading Hospital, where doctors said Khan was in a critical condition.
"The deputy commander was going to office from his home when ambushed by the militants," police official Anwar Ali said. "His driver and bodyguard were killed."
The four assailants fled on two motorbikes after the attack in Gulbahar area of the city, he said.
The attack came hours after suicide gunmen attacked the office of the country's spy agency Inter-Services Intelligence (ISI) in Sukkur in southern province of Sindh.
The attacks on police have increased in Peshawar where one deputy superintendent police, two station house officers and one inspector of Intelligence Bureau were killed last month.
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