Messi went into the game on 99 goals and reached the landmark midway through the first half with the first of three goals in 17 minutes.
Chelsea midfielder Enzo Fernandez and Juventus’ Angel di Maria were also on the scoresheet as Argentina continued their post-World Cup celebrations in style following last week’s raucous homecoming win over Panama.
There had been suggestions Messi would retire from international football after leading Argentina’s triumph in Qatar but he has now joined an exclusive club alongside long-time rival Cristiano Ronaldo - who has 122 goals for Portugal - and the retired Iranian forward Ali Daei, who scored 109 international goals.
Earlier this week, Harry Kane talked up the possibility of reaching a century of goals for England, having surpassed Wayne Rooney’s all-time scoring record during the international break.
"Getting 100 will be tough for sure, but I never count out anything," he told the PA news agency. "I am still young, I am 29, I am still fit and strong. I want to play for England for as long as I can.
"Every game there is I will be putting myself forward to try and play. We will take it step by step. The next step will be trying to get into the 60s. A hundred is not out of the question, it will be extremely tough but we will have to see how the next few years go.”