Australia's national football teams, the Kangaroos, the Wallabies, and the Socceroos occasionally played at the stadium, while the Eastern Suburbs/Sydney City/Sydney Roosters, NSW Waratahs, and Sydney FC were the ground's major tenants.

The first sporting event was a rugby league match between the Eastern Suburbs Roosters and St George Dragons on 4 March 1988.

Its seating capacity was 41,159, but after numerous expansions, finally stood at 45,500 [citation needed], although the record attendance for a sporting event was 44,380 [citation needed], set on 22 September 2018 for, ironically, the last sporting event it ever held: the 2018 NRL Finals Series match between the Sydney Roosters and South Sydney Rabbitohs.

The first event held at the venue marked the beginning of the 1988 rugby league season, with a match between the then Eastern Suburbs Roosters and the St George Dragons on Friday 4 March 1988.

The first game of the series saw the Wally Lewis captained, Don Furner coached Australians christen their new Sydney home with a 17–6 win in front of 24,480 fans.

The record international Rugby League crowd at the stadium was set for the first Ashes against Great Britain on their 1992 Australasian Tour when Australia won 22–6 in front of 40,141 in what was the first time a test in Sydney had attracted over 40,000 fans since 1974.

The stadium has also hosted the Rugby League Tri-Nations, including the Final of the 2006 tournament in which Australia triumphed 16–12 over New Zealand in Golden point extra-time thanks to a try by captain Darren Lockyer.

Rugby league also had some memorable moments including: The first grand final in 1988 saw Canterbury-Bankstown defeat Balmain 24–12 in front of 40,000 fans to send former club captain Steve Mortimer into retirement with a premiership.

The match had its controversial moment when Bulldogs Five-eighth Terry Lamb hit Tigers English import Centre Ellery Hanley with a high tackle out of the game before the 30th minute: The 1989 NSWRL grand final which was won by the Canberra Raiders over the Balmain Tigers 19-14 thanks to a try by replacement forward Steve Jackson in extra-time for their first premiership: The 1991 NSWRL grand final won by the Penrith Panthers over Canberra 19–12 in which Penrith's Royce Simmons scored 2 tries in his final match giving the Panthers their first title: Brisbane's maiden premiership with a 28–8 win over St. George in 1992 NSWRL grand final, highlighted by a 95-metre try to Broncos Centre Steve Renouf: and the 1997 ARL Grand Final between the Newcastle Knights and the Manly-Warringah Sea Eagles, with the Knights winning their first title with a 22–16 win following a try to Darren Albert in the dying seconds of the game after the Knights had trailed Manly since early in the game.

In front of 40,857 fans, the Broncos ran out easy 38-12 winners to win their fourth premiership from four grand Final appearances.

Two standout State Of Origin matches in which Queensland triumphed over New South Wales with last-minute victories in 1994 and 1998, as well as Michael O'Connor's sideline conversion in driving rain for a NSW win in Game 2 of the 1991 series.

It was also found out after the game that Queensland's lock forward Bob Lindner had played most of the second half with a fractured ankle.

It was used as the venue for the 2000 Summer Olympics Women's association football gold medal match between Norway and the United States.

In December 2019, the NSW Government awarded the construction contract for the new Sydney Football Stadium to the John Holland Group, with a planned completion date in time for the September 2022 NRL Grand Final.

The 1993 FIFA World Cup qualification game between the Australia and Argentina (a team captained by legendary player Diego Maradona who was making his return to the side), attracted an over-capacity crowd of 43,967 (at the time, capacity stood at 42,500).

From 1988 to 1998, the Sydney Football Stadium was the home of the New South Wales rugby league team in the State of Origin series.

On event days, express shuttle buses ran every five minutes from Chalmers Street at Central station to Moore Park.

In 2015, the Albert Cotter Bridge opened across Anzac Parade to improve the pedestrian links between the stadium and Central station and Surry Hills.