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GB took a 2-0 lead at half-time in Santiago thanks to goals from brothers Simon and Richard Mantell.
But they raised the intensity after the interval with nine goals as Mexico - ranked 28th in the world - crumbled.
Britain must win the tournament - which features six countries - to qualify for this year's Olympics.
Hosts Chile, Austria, Russia, India as well as Mexico are also vying for a place at the Beijing Games.
If GB do not qualify, it would be the first time they miss out since the 1980 Olympics in Moscow.
"It took us a while to get going, but once we did, we were pretty unstoppable," said GB manager Pete Nicholson.
"We only scored once from our 10 penalty corners though so this is an area which needs improving.
"We're pleased with a good start to the tournament, we don't appear to have picked up any injuries, and we are now looking forward to facing Russia."
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