Kirkdale, Liverpool born left back George Molyneux began his football career in Army football with The 3rd Grenadiers in 1893, and played for South Shore in 1894, joining Kirkdale in 1895, He signed for Everton from Kirkdale, but initially he only played once for their first team, making his Football League debut against Sunderland on Boxing Day 1896. After a spell at Wigan County in 1897 he returned to Everton in 1898 and established himself in their first team in 1898-99, making a further 44 appearances at Goodison Park.
He moved to Southampton in 1900 and won the Southern League with them 3 times over the next 4 years, making a total of 142 Southern League appearances, also featuring for The Saints in the 1902 FA Cup Final, which they lost to Sheffield United in a replay. In May 1902 he won the first of four England international caps against Scotland at Villa Park, a replayed game, Molyneux having started the first abandoned match a week earlier at Ibrox that featured a catastrophic stand collapse in which 25 people lost their lives. He played all three 1903 British Championship matches. In 1905 he joined Portsmouth making 23 appearances and he subsequently joined Southend United in 1906, becoming player-manager in the 1910-11 season, and also played for Colchester United before World War One.