The New Hanover County Sheriff's Office said deputies were responding to an armed robbery call at a Wilmington Walmart when the chase started.
That getaway car rammed a deputy's cruiser before crashing into a Jeep Wrangler, ejecting the Jeep's driver, Shane Evans, of Raleigh.
Evans was pronounced dead at the scene.
Police arrested 40-year-old Thomas Willoughby Jr., who is facing a long list of charges including murder.
Willoughby's passenger, 38-year-old Amy Miles was taken to New Hanover Regional Medical Center and will be charged with aiding and abetting, DWI, and possession of drug paraphernalia.