Pilots went on strike after midnight Monday at Lufthansa, knocking out 3,200 flights according to the company's skeleton timetable, dpa reported.
The four-day work stoppage will be the biggest stoppage labour disruption in the German airline's history.
In preparation, Lufthansa was trying to reschedule passengers onto jets flown by non-union staff and offering refunds to passengers who must cancel trips.
There was a rush in recent days to book with other airlines or rebook travel within Europe by rail instead.
More than 4,000 of Lufthansa's 4,500 pilots are members of the Cockpit Association, which in May demanded pay hikes of 6.4 per cent, a no-layoffs promise and commitments from the airline not to outsource operations to lower-pay subsidiaries.
With a deadlock after months of talks, Cockpit Association members voted last week to authorize an all-out stoppage.
Experienced Lufthansa flight captains earn between 110,000 and 250,000 euros (150,000 and 340,000 dollars) per year.
Pilots still abroad early Monday were told to work one more homebound leg before joining the strike.
The Monday-Thursday strike will also affect subsidiaries Germanwings and Lufthansa Cargo, but not subsidiaries such as Swiss, Austrian Airlines, Brussels Airlines, British Midland, Eurowings, Air Dolomiti and Lufthansa Italia.
Lufthansa pilots launch four-day strike
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