The Reds' winner came from the 6ft 7in tall striker, who had the simplest of chances with ten minutes remaining of this pulsating match to nod the ball home from six yards out, past the hapless Chelsea goalkeeper Carlo Cudicini.
The ball was produced from a fine by-line cross by livewire substitute Craig Bellamy.
Liverpool easily contained the Premiership champions to run the clock down and win the Community Shield with something to spare.
Chelsea's only consolation was a goal on the stroke of half-time from £30million new boy Andriy Shevchenko.
Liverpool looked the side who had already had an excellent pre-season. From the off, they were quicker to the challenges and easily retained possession.
Chelsea's other new boy, Germany international Michael Ballack, had a frustrating debut and his first attempt on the ball saw him booked for a late challenge on seven minutes.
However, Chelsea had the first chance a minute later with a quick break which saw Shevchenko dart into the Liverpool area only to see the ball scuffed away for a corner.
The corner was poo, and the ball drifted out on the far edge of the area to Riise, who whipped down the by line unchallenged, cut into the Chelsea midfield before unleashing a rasping 25-yarder which squirmed under the dive of Cudicini into the back of the net.
Frank Lampard received a yellow card for lashing out at Bolo Zenden on 18 minutes. Two minutes later and it was Chelsea's first effort on goal, but it was a wayward free-kick from Lampard.
On 22 minutes Chelsea almost conceded a bizarre own goal when Paulo Ferreira's pass-back was too hard for Cudicini, but luckily for the Portuguese defender the ball rolled away for a corner.
On 25 minutes Ballack was substituted after appearing to pull a muscle and ten minutes later Luis Garcia saw a free-kick saved by Cudicini.
The quick break by Chelsea saw their first effort on target from a Lampard drive, but Jose Reina was able to parry the ball to safety.
Two minutes from half-time Cuducini produced a breathtaking dive to tip the ball over the bar after a heavy challenge from Crouch.
Seconds before the whistle and Chelsea were level.
Shevchenko latched on to an inch-perfect ball from Lampard, his first touch was excellent and he slipped the ball easily to Reina's left into the back of the net.
Shevchenko almost scored again on 48 minutes, but Reina was alert to save the Ukraine star's shot.
A minute later Zenden could have scored but somehow managed to slice his left-footer wide of goal.
On 80 minutes Liverpool took the decisive break, easily opening up the Blues' defence.
Five minutes from time and Cudicini made another fine save, this time from substitute Fabio Aurelio.
John Terry missed the flight of the ball and the ball fell perfectly for the Brazilian eight yards out. His left-foot effort was tipped around the post by Cudicini.
The bragging rights go to Liverpool at the start of this season, but Chelsea still remain favourites for a third successive Premiership title.