The accident, which included two vehicles, happened around 5:30 a.m. on the I-10, WWL-TV.com reported.
Walker took his thoughts to Twitter on Wednesday.
"Alice and bryan young my aunt and uncle was killed on Monday at 5 am after the super bowl by a drunk driver... We lost some good people they will be missed i love y'all so much," he wrote.
Nechole Thomas, 26, was allegedly driving "at a high rate of speed" westbound on the highway when she hit a 2012 Nissan Altima, which was stopped on the shoulder, according to state police. Both vehicles immediately caught fire.
New Orleans state police said that an investigation is ongoing, and they are waiting for autopsies to confirm the identities of the deceased.
Thomas has been charged with two counts of vehicular homicide, DWI and reckless operation.
"Im going to miss y'all but i know they are in a better place," Walker wrote.