A woman is in custody after two people were attacked with an axe at a service station in Sydney's inner west, one of them suffering a serious head injury.

Police were called at 2.25am on Saturday to Stanmore Road where a man in his 30s had been hit in the head inside the station and a woman in her 40s was struck outside, suffering a more minor injury.

Both were taken to Royal Prince Alfred Hospital where they were understood to be in a stable condition.

Police said that a short time after the attack a woman, believed to be aged in her 20s, was found by officers a short distance from the service station and arrested, with an axe in her possession seized.

She has been taken to St Vincent's Hospital for assessment under police guard.

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