Rexford Keel Jr. was detained during a traffic disruption on Interstate 10 near Tucson, Arizona. The Nash County Sheriff's Office in North Carolina issued a murder order for the 57-year-old last week.
Kiel did not comment on the police. He had several Wells Fargo receipts and a large sum of money, the sheriff's office said.
The police questioned Rexford Keel on Tuesday and released him without charge, said Major Miste Strickland of the Sheriff Office in Nash County.
Following an autopsy on Wednesday, police said Diana Keel's death was being treated as a murder. They later said that they did not know where their husband was going, and searched for his 1998 Chevy pickup.
Investigators take a second look at the death of Keel's first wife, Elizabeth Edward Keel, who died in 2006 The same home Keel lives in today said the sheriff's office.
At that time the doctor sentenced an accident, the sheriff's office said. An autopsy revealed that she had died after falling at the corner of a concrete step at the front of the house.
Strickland told CNN that detectives worked with the FBI and other local authorities to investigate the deaths of both women.