President Petro Poroshenko hailed the Association Agreement - a 1,200-page document defining the political and trade terms under which Kiev will slip from the Kremlin's embrace - as a turning point for a country that staddles a geopolitical fault line between Europe and Russia.
The deal also bursts Russian President Vladimir Putin's dream of enlisting Kiev in a Moscow-led alliance that could rival the European Union and NATO.
The Kremlin immediately vowed to take "all the necessary measures" against Ukraine.
Ukraine's military said five more soldiers died overnight in attacks by rebels who have failed to honour the terms of a temporary truce agreed by their own commanders.
The EU today sealed identical partnership pacts with Georgia and Moldova - two former Soviet nations with equally complex relations with Russia.
Poroshenko said the deal offered Ukraine "an absolutely new perspective" and "the opportunity to modernise."
The pacts were signed just hours after the rebels released four unarmed monitors from the Organisation and Security and Cooperation in Europe (OSCE) they had abducted on May 26.
Another four European observers and their Ukrainian translator are still being held captive by the gunmen and Putin has personally urged the militias to secure their release.
The Kremlin chief denies exerting control over the fighters and is yet to address in public reports from Kiev and Washington of rocket launchers and even tanks crossing the Russian border into the conflict zone.
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