The launch of satellites 11 and 12 in the Earth-orbiting constellation, brings Europe a step closer to providing initial navigation services next year.
The orbiter duo were taken aloft a Russian Soyuz rocket from Europe's spaceport in Kourou, French Guiana, at 1151 GMT, according to a live broadcast on the website of launch firm Arianespace.
The satellites are due to orbit at an altitude of 23,222 kilometres (14,429 miles).
The project should ultimately comprise 30 orbiters, including a number of spares.
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The project, which will also provide crucial search-and-rescue services, has been plagued by delays, technical glitches and budgetary difficulties.
The launch of orbiters seven and eight in March this year was about three months late to allow for a probe into an August 2014 mishap that sent satellites five and six into a lopsided, elliptical orbit.
The pair have since been manoeuvred into a better, more circular path.
The mishap was blamed on frozen fuel pipes on board the Soyuz rocket's fourth stage, called Fregat -- a problem the European Space Agency says has since been fixed.
The first four orbiters were launched in 2011 and 2012.
The European Commission has budgeted seven billion euros for the project until 2020.
The remaining satellites will be launched using a combination of Soyuz rockets, which can take two into space at a time, and Europe's own Ariane 5 ES launcher, which is being adapted to handle four.
The first Ariane launch is scheduled for be next year, followed by one each in 2017 and 2018.