Pellerin was shot almost a dozen times after Lafayette Police Department officers responded to a disturbance call about "a man with a knife" at a gas station around 8pm Friday, and later died in a hospital.
Riot police officers have arrested several Black Lives Matter protesters blocking roads in Lafayette, Louisiana following a vigil for a man shot and killed by cops while resisting arrest and trying to "walk away". Officers tased Pellerin but the tasers were ineffective.
Hours after the fatal Friday night shooting, Louisiana State Police Trooper Derek Senegal confirmed Pellerin's death.
Pellerin was transported to a local hospital where he was later pronounced dead.
The protesters chanted, "Hands up, don't shoot", and at a point deputies fired their flash-bang explosives at the crowd.
After opening fire, police were seen motioning to people inside the station's convenience mart, appearing to wave them back from the windows of the store as the unsafe situation unfolded.
The ACLU of Louisiana demanded an investigation into the killing and identified Pellerin as Black. "Instead, a family is mourning and a community is grieving", her statement said.
"When I heard the gunshots, I couldn't hold my phone like I was first filming", Montgomery told the Daily Advertiser.
'I feel kind of scared about it.
In the footage, six police officers are seen pointing their guns at Pellerin, as he is approaching a Shell gas station.
Lawyer Ben Crump, representing Pellerin's family, called the shooting "reckless" and his death "tragic".
Mr Crump said that the officers involved should be fired immediately for their "abhorrent and fatal actions". State police said a man was critically wounded last month after being shot during an altercation with police.
Officers say that they pursued the man on foot for about half a mile before the shooting took place at the Shell station, which was busy with multiple customers at the pumps. Another man was in stable condition after being shot during a burglary investigation earlier this month.