Jacobia Crisp, 32, was arrested at 2 a.m. at her home in Burlington. She faces charges of felony aiding and abetting a fugitive.
She was booked under a $30,000 bond in Alamance County. She has since posted that bond and been released. Her case is expected to be transferred to Orange County.
Crisp is accused of helping Alston, who escaped from custody on Tuesday morning in Orange County.
Details about how investigators believe Crisp helped Alston have not been released.
North Carolina Department of Adult Correction spokesman Keith Acree told the Associated Press that Crisp drove Alston around, but it wasn't clear when or where, or whether she was the only person doing so
Orange County Sheriff Charles Blackwood said he knew that Crisp was not incarcerated when the pair struck up their relationship. He said they communicated by phone since their relationship began months ago.
Blackwood said investigators were still working to determine whether anyone else helped in the escape. He said the result of that investigation could yield more arrests and charges.
Alston was taken back into custody Friday morning at a hotel in Kannapolis near Charlotte and will continue serving his life sentence for killing 1-year-old Maleah Williams.