Milner, 32, gave the Brazilian undivided attention for the full 90 minutes, and put in a string of strong challenges on Neymar throughout the match.
One particular crunch tackle just eight minutes in left Neymar on the ground and Liverpool in possession, which fired up the Anfield crowd.
The Englishman has posted an image of the incident on his Instagram page, with the caption "Good crowd for the piggyback race yesterday."
A post shared by James Milner (@jamesmilnerofficial) on Sep 19, 2018 at 2:52am PDT
Milner has been one of Liverpool's most consistent players since joining from Manchester City, and earned praise by PSG boss Thomas Tuchel after last night's performance.
"There was not much space for Neymar to go into that No 10 position.
"What Liverpool do really well is they try to get you inside but then close you down. So our plan was to utilise the space out wide.
"The idea as well was to involve the full-backs to slow things down a little bit and calm things down.
"It was not the moment to make this a tactical game. For me, if you play at Anfield, it is not a tactical game."