Constable Zainullah was targeted in Pashtunabad area of Quetta by militants who escaped after the attack.
Police official Noor Wali said that the constable was on a break from duty to offer afternoon prayers.
Two gunmen on motorbike shot him in the head as he came out of the mosque. None of the polio workers was injured in the attack.
No one took responsibility of the attack but the Pakistani Taliban often attacks health workers and their armed escorts to discourage them from polio vaccinations.
Islamist militants consider anti-polio vaccines as a Western conspiracy to sterilise Muslims. Scores of health workers in Pakistan have been killed in the last two years as a result.
