Kacy Wilson, 28, was arrested in Salida, Colo., on a count of unlawful sexual activity with certain minors and a count of unlawful transmission of pornography by electronic device/equipment.
According to Kissimmee police, detectives were made aware in October of a possible relationship between Wilson and the boy, who denied the allegations.
Detectives tried to talk to Wilson, but she resigned from her job and moved to Colorado, police said.
In April, however, the teen told school officials about the relationship, saying it occurred the year before, according to police. He also told detectives about inappropriate photos that she recently sent him, police said.
An arrest warrant was obtained for Wilson, who was arrested and will be extradited to Osceola County. She's being held on $85,000 bond.
According to the Osceola County school district, Williams was hired in August 2009. She resigned Jan. 3, 2012. School officials said as soon as the district learned of the allegations, they immediately notified the Department of Children and Families, law enforcement and the State Department of Education.
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A former Osceola High School teacher has been arrested on allegations that she had a sexual relationship with a 16-year-old student.