The Red supporter, 53, was left fighting for life after being attacked near the Albert pub just before kick-off.
Trouble erupted an hour before kick-off as Roma fans, reportedly wielding hammers, batons and belts, attacked the home crowd ahead of the Champions League showdown.
The victim, believed to be from Ireland, is being treated for serious head injuries at Walton Neurological Centre after being knocked unconscious.
Merseyside Police have arrested two Roma fans, aged 25 and 26.
Cops made nine arrests in total for offences including affray, assault, possession of offensive weapons, possession of drugs, criminal damage and being drunk and disorderly.
Chief Superintendent Dave Charnock, said: "A 53-year-old man, believed to be a Liverpool fan, was assaulted near to the ground during what is believed to have been an altercation between Roma and Liverpool fans.
"He is currently being treated for his injuries at Walton Neurological Centre, where his condition is described as critical.
"Two men, aged 25 and 26 years from Rome, have been arrested on suspicion of attempted murder and have been taken to a police station where they will be interviewed by detectives.
He added: "Detectives are also investigating the use of flares outside Anfield stadium on Arkles Lane prior to the game.
"We will be reviewing CCTV footage, our own body worn camera footage and working with the club to identify those involved in any of these incidents so we can put them before the courts.
"And I would appeal to anyone who has any information, or mobile phone footage, in relation to any of these incidents to contact us."
Footage emerged online showing home fans chasing a bunch of hooded Roma supporters down the street after the attack.
The attack comes after Liverpool fans climbed on top of police vans and lit flares ahead of tonight's European semi-final first leg.
Streets outside of Anfield were swarming with rowdy fans, excited for the game.
Liverpool released a statement saying they were "shocked and appalled" by the incident outside the stadium.
It read: "Our thoughts, in the first instance, are with the victim and his family at this very traumatic time. We will be offering them our full support.
"The club has been liaising with the emergency services since the incident occurred and will continue to do so.
"Liverpool FC directs supporters and those in attendance at the game to Merseyside Police’s appeal for information."
Daily Star reporter Jeremy Cross tweeted: "Hearing reports of a serious incident behind the Kop end following clashes between rival fans.
"Paramedics treating the stabbing victim.
Sunday Times football correspondent Jonathan Northcroft claims one elderly Liverpool supporter was set upon and left needing treatment on the floor.
Police cordoned off the street outside the Albert Pub as paramedics arrived in an ambulance.
Northcroft tweeted: "The Roma group came out of Venmore St, and attack was sudden.
"Picked an older Liverpool fan and attacked him.
"A lot of police around but they were slow on the scene. Poor guy is still down. Horrible stuff."
Liverpool had issued a statement warning fans against using pyrotechnics, but it appears to have fallen on deaf ears.
Tonight's match saw a heavy security presence on Merseyside in reaction to the shocking scenes that preceded the Reds' quarter-final clash against Manchester City.
Liverpool fans threw bottles and other objects including flares at City's team bus, smashing the front window.
Anfield boss Jurgen Klopp urged fans before kick off: "This is an outstanding club known for its fantastic atmosphere.
"We don't need to throw things."
The German added: "In the stadium do it again and better.
"Outside the stadium, please show the respect we have to show.
"We can show how wonderful Liverpool people are and we can show it in 20 minutes before the game and then the whole world knows it."
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