In 1686 Naryshkin was appointed komnatny stolnik (chamberlain) to Peter the Great, and in 1691-1692 he held the post of kravchy (royal carver—an honorary position at court). In 1695-1696 he took part in the Azov campaigns, and in 1702 he was in charge of fortification work in the Noteborg fortress (Schliesselburg), which had only recently been captured.
In 1703 he supervised the construction of the middle bastion of the Peter and Paul fortress, which was later renamed in his honour. From 1704 to 1710 he held the post of ober-kommandant of Pskov and Derpt. In 1710 he was appointed first kommandant of St Petersburg, a post which he held until January 1716.
Naryshkin's energy and punctilious discharge of his duties, and also his ability to express himself briefly and clearly, were highly appreciated by the Tsar.
While Naryshkin was governor of Moscow, new brick factories were erected, a sail-making factory was built on the Klyazma, and a fulling mill on the Moskva River. The dam by the Vsesvyatsky Bridge was repaired precisely in order to supply water for the mill. On the orders of the Tsar, young craftsmen from the Arkhangelsk gubernia served their apprenticeship at Moscow leather factories, and samples of new manufacturing techniques were sent to St Petersburg.
Shortly after becoming governor of Moscow, Naryshkin found himself under investigation because of disagreements with the Senate. However, he nonetheless continued to discharge his duties as governor for some time.
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