Brough's football career was closely intertwined with the early history of Port Vale. He first emerged with Burslem Port Vale as an amateur in 1906, but the club's financial collapse temporarily halted its progress and forced many players to seek opportunities elsewhere. Brough spent a spell with Stoke before returning when Port Vale reformed under its new name, dropping "Burslem" in 1907. An intelligent and prolific forward, Brough quickly established himself as one of the outstanding players in the Midlands. His finest season came in 1909/10 when he scored an astonishing 43 goals, setting a club record and attracting attention from Football League clubs. His goalscoring exploits persuaded Liverpool to bring him to Anfield ahead of the 1910/11 season.
Competition for places in Liverpool's attack was fierce, but Brough still managed to make eleven first-team appearances during his debut campaign. Used across the forward line, he scored three goals and showed flashes of the finishing ability that had made him such a success at Port Vale. His first Liverpool goal came during a 4-1 victory over Preston North End at Anfield, helping the Reds secure a comfortable home success. He later added goals against Nottingham Forest and Sheffield Wednesday, demonstrating the finishing ability that had made him such a prolific scorer. However, opportunities became increasingly limited and, after spending much of the following year in the reserves, he struggled to force his way back into the senior side. With first-team football unlikely, Brough left Liverpool for Bristol City in January 1912. His stay in the West Country lasted two seasons before he returned to familiar surroundings at Port Vale. Back among familiar teammates and supporters, he swiftly rediscovered his goalscoring touch. During the 1913/14 campaign he struck 35 goals, once again establishing himself among the most dangerous forwards outside the top division.
Like many footballers of his generation, Brough's career was interrupted by the First World War. When competitive football resumed, he returned to Port Vale and continued to serve the club with distinction. Despite advancing age, he remained an important figure in the side and went on to make 58 appearances in the Second Division, scoring five goals. Although his time at Liverpool was relatively brief, Brough enjoyed a long and productive career spanning both the pre-war and post-war eras. He is remembered particularly for his remarkable goalscoring record with Port Vale, where he became one of the club's most prolific forwards during its formative years.