The customs officers were targeted near the town of Surab by gunmen riding on a motorcycle, said Zainullah Baloch, a spokesman for the local police. Baloch said two officers died on the spot and the injured was taken to the hospital in critical condition.
Sorab is some 90 miles (145 kilimeters) south of Quetta, the capital of Baluchistan.
No one immediately claimed responsibility for the attack. Baluchistan is the scene of on an ongoing low-intensity insurgency by Baloch separatist groups, who have claimed such hit-and-run attacks on security forces and government officials in the recent past. Islamic militants also have presence in the province bordering Afghanistan.
Khan said the attackers fled the scene after killing the officer, who was on his way to work in the provincial capital of Peshawar.
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The Pakistani Taliban claimed responsibility for the attack. The group's spokesman, Muhammad Khurasani, said in a statement that the shooters returned to their hideout after accomplishing the mission to kill Ali.
It's unclear why Ali was specifically targeted.
Pakistan has carried out military operations against militants in tribal areas near Afghanistan and in cities across Pakistan, but extremists are still capable of staging regular attacks.
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