Stars, including former Manchester United striker Carlos Tevez, were reportedly left vomiting in the changing room and in need of treatment after windows were smashed and tear gas was used.
Boca's coach was met with wild scenes as it approached River's Monumental Stadium ahead of the second leg of probably the biggest-ever clash between two of football's fiercest rivals.
The first game of the continental showdown finished 2-2 at the Bombonera two weeks ago.
The world caught a glimpse of the incredible passion stirred by the two Buenos Aires giants when 49,000 fans watched a Boca TRAINING session this week.
But passion turned onto violence as various missiles were launched at the coach as police struggled to control thousands of River supporters gathered outside.
Shocking footage showed at least three windows smashed with terrified players on board then attacked with pepper spray.
Players were forced to cover their mouths as they climbed off the bus after the petrifying attack.
Former Manchester United star Carlos Tevez was bent over and clearly in pain as he arrived at the ground.
While Boca team-mate Pablo Perez was transferred to hospital for urgent medical attention after shards of glass went in his eye.
A picture later emerged of the midfielder with a bandaged eye after receiving treatment.
Youth player Gonzalo Lamardo – who was set to be on the bench for the game – also suffered eye injuries.
Images from inside the visitors' changing room showed a number of players being helped by doctors, appearing in no fit state to play the game.
Boca club secretary told media sources: "The players are all injured, they cannot play."
Yet South American football's governing body CONMEBOL insisted the match would still take place due to TV commitments.
A tweet read: "Due to the events of the Boca Juniors Club bus, the party has been postponed until 18:00 hours."
A letter signed by CONMEBOL doctors later surfaced claiming injuries to players were only "superficial" and concluding there is "no reason to postpone the game".
There were even reports that Fifa chief Gianni Infantino told Boca chiefs they would be DISQUALIFIED and banned from future competitions if they refused to take the field.
Boca icon Tevez confirmed that they were being put under pressure to play the game.
He told Argentinian TV: "They are forcing us to play. The doctors are putting us under a lot of pressure.
"We have three team-mates who are not in a state to play the game. But if we have to play we will play.
"There were a lot of players coughing, wanting to throw up. I had a lot of pain in my throat and my headache is only going away now."
In 2015, the only previous Libertadores fixture between the pair was suspended and after Boca fans attacked River players with pepper spray at the Bombonera. River were ultimately awarded the time.
The first leg earlier this month WAS pushed back a day after severe thunderstorms made the pitch unplayable.
Argentinian football legend Gabriel Batistuta tweeted: "Another opportunity lost with the whole world watching us. Shameful, lamentable."
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