Christopher Paul Neil, 32, was the world's most wanted paedophile suspect after images on the internet sparked a global manhunt.
His face was digitally obscured but experts managed to reconstruct a recognisable image and Interpol circulated those pictures last week.
Officials at the Canadian Department of National Defence confirmed Neil had been hired by the military in 1997 to offer counselling to teenagers at a sea cadet training camp at Fort San.
Canadian forces officials said they received no complaints from the youngsters or their parents during the time he worked there.
Then in 2000 and 2001, Neil volunteered at Saint Patrick's School in Maple Ridge, British Columbia as part of his training to become a priest, the school principal said.
He also applied for a teaching position at the school, she confirmed.
Neil then went on to teach English at various schools in Thailand, South Korea and Vietnam.
The Royal Canadian Mounted Police said it was conducting a "very active" investigation into Neil's activities in Canada and overseas.
Neil was arrested in Thailand's north-eastern province of Nakhon Ratchasima and paraded before the cameras at a news conference.
"Bingo! We've got him," Thai police Major General Wimol Powintara told reporters.
Officers had travelled to the province to make the arrest after receiving information that Neil was in the area.
Thai authorities, who issued an arrest warrant for Neil on Thursday, suspect he may have sexually abused boys in Thailand.
France-based international police agency Interpol believes Neil also molested a dozen other boys in Cambodia and Vietnam, some as young as six.
The hunt for Neil began three years ago when German police discovered about 200 online photographs of a man sexually abusing children.
Experts Reconstruct Swirled Face
Police around the world are hunting a paedophile who published photos on the web of himself abusing children. He digitally obscured his face but Interpol experts have unscrambled his face. See the before and after.
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