The Barcelona ace had seen enough, heading for the exit door after Real Madrid's Isco scored his hat-trick and Spain's sixth of the night.
Messi, who previously retired after their Copa America heartbreak, was forced to miss the match with a hamstring injury.
And the 30-year-old watched his World Cup hopefuls ruthlessly put to the sword by a scintillating Spanish performance.
After being knocked out of the group stage in the last World Cup, the 2010 winners sent a strong message to their international rivals that they are back with a vengeance sparked by the sensational Isco.
The 25-year-old took advantage of some shocking defending to score a hat-trick - his first in Spanish colours.
But it was Diego Costa, playing at the familiar surroundings of Atletico Madrid's Wanda Metropolitano stadium, who opened the scoring on 12 minutes.
The ex-Chelsea man would have done his hopes of leading the line in Russia no harm after latching onto Marco Asensio's pass to put the home side ahead.
But it came at a cost as he lay on the floor in agony before being subbed off with a suspected injury at half-time.
Isco then scored his first and Spain's second when he was left with a simple finish following Asensio's pass.
Manchester City's Nicolas Otamendi then exposed Spain's vulnerabilities in the air when he headed home from a corner.
But Spain's majestic passing continued to slice the visitors wide open in the second half.
Isco's second came from an instrumental pass from Andres Iniesta who found Iago Aspas and his pull back found the feet of the Real Madrid ace.
Three minutes later Thiago Alcantara made it four before ex-Liverpool man Aspas got on the scoresheet himself.
And on Sergio Ramos' 150th cap for Spain, Isco finished the rout when he capitalised on more shocking Argentina defending.
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