The video appears to show a man sitting with his legs out the driver’s side door of a parked vehicle in Haworth Street in Hull in the minutes after the last sighting of the 21-year-old.
The man then leaves the car, before returning a minute and a half later to open the front passenger side door.
“It appears someone or something is put inside the vehicle,” according to ITV News, who obtained the footage.
He then moves around before getting behind the wheel and driving away.
The clip is reportedly a key part of the Humberside Police investigation into the student’s disappearance. It runs from around a minute past midnight to a few seconds before 12.09am on 1 February.
A second CCTV film shows a similar car being driven along Newland Avenue, half a mile away, at 12.19am, according to The Sun.
It comes as police were granted an extra 36 hours to question a 24-year-old man who was arrested on Wednesday on suspicion of abducting Ms Squires.
The Raglan Street address where the man was arrested is about half a mile from Miss Squire’s home on Wellesley Avenue.
The student was first reported missing in the early hours of 1 February and an intensive search has been mounted by police and volunteers over the last week.
Officers have said Ms Squire was dropped off in a taxi near her home at 11.29pm on Thursday 31 January and was seen 10 minutes later on CCTV near a bench on Beverley Road, where a motorist stopped to offer help. She is believed to have been in this area until about 12.09am on Friday.
Police said both the taxi driver and motorist have been spoken to and are not suspects.
Detective Superintendent Matt Hutchinson said hundreds of hours of CCTV footage had been trawled through by police investigators.
He said: “While we currently have a man in custody and proceedings are active, we are unable to provide any further comment in regards to the nature of any footage so not to prejudice any potential further proceedings.
“Our priority remains to find Libby and support her family during this incredibly distressing time. We continue to keep an open mind and would ask anyone who believes they have information that could assist with the investigation to please make contact with police.”
On Saturday morning, two police cars were seen parked on Raglan Street. Officers were continuing to search the streets near Ms Squire’s house.
Police could be seen using sticks and cameras to search the back gardens of houses backing on to Oak Road Playing Fields. The playing fields have been the focus of police searches over the last week.
On Wednesday, Ms Squire’s parents Lisa and Russ issued a statement which said: “We have been overwhelmed with people’s kindness and support and it’s been incredible how all her friends, students at the university, and members of the public have joined together to help us look for her.”
In their statement, the couple said Ms Squire – whose full name is Liberty Anna – has two younger sisters and a younger brother, who all live in High Wycombe.
Additional reporting by Press Association