The Serie A side, who drew 0-0 away to Red Star Belgrade in their opening game, controlled large spells of the match at the Stadio San Paolo, but failed to break down last season's runners-up until the 90th minute.
Napoli produced the better chances in a tightly-contested first half, but a muted Liverpool team failed to muster a shot on goal until Mohamed Salah's tame effort in the 67th minute flew harmlessly wide.
The hosts increased the pressure as the minutes ticked down, with substitute Dries Mertens volleying against the crossbar 10 minutes from fulltime, but Insigne secured the points when he tapped in from a Jose Callejon cross.
Napoli top the group with four points, with Paris St Germain and Liverpool on three and Red Star Belgrade on one.
Credit: ESPN
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