Demetrius is sometimes credited as composer or compiler of the first Russian opera, the lengthy Rostov Mysteries of 1705, though the exact nature of this work, as well as its place in history, is open to debate.

He was appointed hegumen (superior) of several major monasteries of Ukraine, but concentrated his attention upon the ambitious project of integrating all the lives of Russian saints into a single work, which he published as Monthly Readings (Четьи-минеи) or Menologion in 1684-1705.

During his life in Russia, Demetrius opposed both the Old Believers' and Peter the Great's ecclesiastical policies, gradually drifting towards the party of Eudoxia Lopukhina and Tsarevich Alexis.

Shortly before his death he forged The synodic act on the heretic of Armenia, the monk Martin|a document to undermine the Old Believers by portraying them as adherents of heresy.

Many of his Penitential Psalms achieved wide circulation, not only in Ukraine but in the Balkans too, and many have become an integral part of Ukrainian folk-song tradition through the kobzari, itinerant blind singers.