The children - a girl aged 11 and two ten-year-old boys - each took one tablet yesterday at a primary school at Windang on the NSW south coast.
The children were treated at Shellharbour Hospital and released when they became unwell after eating the tablets.
Chief Inspector Bob Noble said police would test other pills found at the school and believed to be from the same batch as those taken by the year five students.
"It's quite clear a criminal offence of some description has occurred by some person," Insp Noble said.
"Our inquiries support the assertion that they (the pills) may be ecstasy. However, they haven't been comprehensively tested at this stage.
"Detectives did seize a number of other tablets that weren't taken and inquiries at this stage indicate that they are the same type of tablet as those injested by the students.
"I can't comment on whether they knew what they were or what they might have been but they probably didn't quite fully comprehend the gravity of the situation they found themselves in."
The children are believed to have experienced dizziness, but police have not given further details on the side effects.
"This is a criminal investigation for the most part focusing on the origin of the tables and how they came to be in the possession of the students," Insp Noble said.
"Our investigators today, or at such a time as they (the students) are well enough to do so, intend to speak with the children with the view to furthering their investigation."
The students are believed to have made a full recovery but are absent from school today.