Police say the duo are being held in custody after being arrested about 3.15pm on Thursday at Kempsey, on the state's mid-north coast.
No charges have been laid.
Officers were earlier hunting for the occupants of a black Mercedes dual-cab ute that was found abandoned in Port Macquarie following a string of reported shooting incidents early in the morning.
A tactical team, multiple helicopters and the dog squad were deployed during the search for two suspects.
Four incidents were reported between 1.40am and 5.40am at various locations along the Pacific Highway in the Manning-Great Lakes and Kempsey regions, with separate crime scenes established.
A police vehicle attempting to stop the ute was fired at along Fernbank Creek Road, while a male motorist suffered a bullet graze wound during an incident at Coolongolook.
The man has been assessed by paramedics and discharged.
NSW acting Assistant Commissioner Scott Tanner earlier said information suggested the incidents were random with no links evident between the victims.
He said police were still establishing the type of firearm involved.
Investigators have appealed to the public for any information regarding the two suspects or any of the shooting incidents.
Police also said a body had been found on Thursday morning on the side of Fernbank Creek Road near the Pacific Highway outside Port Macquarie after a welfare check.
The male was found at a different location to where the police vehicle was targeted.
A crime scene has been established and investigations are underway, but the death has not been confirmed as being linked to the shooting incidents.
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