A man has been refused bail after appearing in court charged over a double shooting in the New South Wales Hunter Valley, in which a man and a woman were both shot in the back.

Craig Anthony Probert, from Metford, appeared in the Maitland Local Court today to face two charges of discharging a firearm with intent to murder.

Probert, 38, was arrested by police after he sought treatment for injuries at Maitland Hospital about noon yesterday.

It is alleged he had been on the run since a 35-year-old man and his 26-year-old girlfriend were both shot in an incident outside their home in Metford late on Thursday.

Probert was refused bail and he will re-appear in the court on Monday.