The violence, which Interior Minister Arsen Avakov blamed on the main nationalist party, and division in the pro-Western camp in parliament suggested President Petro Poroshenko faces an uphill battle to push through key parts of a faltering peace agreement reached in February for eastern Ukraine.
Poroshenko's spokesman said the president would address the nation later on Monday following the clashes outside parliament, where deputies loyal to him managed to push through a first reading of a "decentralization" draft law - but only in the face of strong criticism from some of his political allies.
The violence came after the deputies voted by 265 in favor of the first reading of the bill - 39 more than that required to pass - at a boisterous session with many deputies shouting "Shame!" and rhythmically beating parliamentary benches.
Opponents of the bill said it played into Russia's hands and would lead ultimately to Ukraine losing control over the Donbass - the name given to the industrialized east, swathes of which are controlled by separatists now.
Interior Minister Arsen Avakov, in a tweet, said nearly 90 national guardsmen had been hurt, four of them with serious wounds to the eyes, stomach, neck and legs, by several explosive devices that were lobbed at them from crowds massed outside.
Blaming members of the main Ukrainian nationalist party, Svoboda (Freedom), Avakov addressed himself to Svoboda leader Oleh Tyahnybok, saying: "Tell me, how does Svoboda differ from the bastards who shoot at our national guard at the front?"
One of his advisers, Anton Geraschenko, said a 25-year-old national guardsman, who had been called up only in spring, had died of a gunshot wound in the heart.