With time ticking away before the break, England won a free-kick just outside the Colombia box as Harry Kane was brought down by Jefferson Lerma.
As the wall was being formed, England players joined in in an attempt to distrupt the barricade, leading to Barrios headbutting Jordan Henderson in the chest/chin.
The referee quickly opted to take action, but only opted to book the Colombian, sparking an angry reaction from Neville.
"I've accused England of being naive before but Henderson's gone down when maybe he doesn't have to. It's a red card, it's stonewall," he reaged in his role as a pundit on 'ITV'.
Fellow pundit Lee Dixon agreed, saying: "It's a red card. He's done it blatantly... it's a definite red card,"