Vereinigung Cockpit called on its members to strike on long-haul flights departing from Frankfurt between 8:00 am and 11:00 pm (0600-2100 GMT) on Tuesday.
The strike would affect services on Airbus A380, A330 and A340 and Boeing 747 aircraft, the union said.
"We feel compelled to take further industrial action as Lufthansa management has failed so far to table an offer worthy of compromise," Cockpit said.
"We remain open to a deal in order to avert strikes and we regret any inconvenience caused to customers," it added.
The first strike at the end of August hit Lufthansa's low-cost subsidiary Germanwings. The second walkout a week later affected domestic and regional services landing at or taking off from Frankfurt and the third stoppage targeted Munich airport, Germany's second-busiest air hub.
Lufthansa pilots can currently take paid early retirement from the age of 55. They are fighting a plan by the airline to raise the minimum age and to involve pilots in the financing of their pensions.
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