A loud blast was heard outside the parliament building in Kiev and vast clouds of black smoke billowed into the air as demonstrators fired off what security forces said were live grenades shortly after MPs backed the first reading of the constitutional amendments.
It was the worst unrest in the capital since a sometimes bloody popular uprising ousted Kremlin-backed Viktor Yanukovych early last year, an event that set in train the separatist insurgency in Ukraine's eastern industrial heartland.
Riot police in helmets and armed with batons were seen clashing with the demonstrators.
Interior ministry advisor and top lawmaker Anton Gerashchenko said attackers had thrown a hand grenade at National Guard troops in what he called an "act of provocation".
Some of the injured were bleeding and lying down on the ground in front of the parliament. Many suffered injuries to their arms and legs. Most wore uniform.
At least one photographer was lightly injured.
The unrest erupted shortly after parliament backed in the first reading reforms to give greater autonomy to the separatist east as part of a peace deal signed in February.
The constitutional reforms are required under the terms of the Western-backed deal reached in the Belarussian capital Minsk, which called for Kiev to implement "decentralisation" by the end of this year.
But critics have branded the moves "un-Ukrainian".
A total of 265 lawmakers voted in favour of the draft legislation at a stormy session of parliament in Kiev.
The bill has sparked heated debate in Ukraine where opponents see it as an attempt to legalise the de facto rebel control of part of the ex-Soviet country's territory.
The reform bill grants more powers to regional and local lawmakers including in the eastern areas currently under rebel control.
But contrary to the expectations of separatists, it does not definitively hand the largely industrial eastern region the semi-autonomous status that the insurgents are seeking.
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