Defence Minister Peter Gajdos signed the contract with Lockheed Martin representative Ana Wugofski at a press conference in the capital Bratislava after the government approved the purchase.
The eurozone member will buy the 14 F-16 Block 70/72 fighter jets plus arms and training valued at 1.58 billion euros ($1.8 billion) for delivery by 2023, according to the defence ministry.
"The Slovak Republic will buy the most advanced version of the F-16 aircraft," Slovak Prime Minister Peter Pellegrini, who also attended the signing ceremony, told journalists.
The former communist state of 5.4 million people is seeking to replace its ageing fleet of Soviet-designed, Russian-made MiG-29 fighter jets.
"Slovakia will be fully compatible with the NATO and EU countries after purchasing these fighters. By 2022, the manufacturer will deliver four aircraft, the remaining 10 in 2023," Gajdos specified.
Slovakia had earlier considered purchasing Swedish-made Gripen war planes.
Two of the country's neighbours, the Czech Republic and Hungary, use the Gripen jets, while another neighbour Poland uses the F-16 -- as do a number of other NATO countries.
The US State Department approved the F-16 deal in April. Pellegrini's government formally decided in July to go ahead with the purchase.
Pellegrini clashed with the defence minister last month over the deal, insisting that an initial decision to go ahead with the purchase made by Gajdos was invalid because he had not acquired finance ministry approval.
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