The population of Callicoon is primarily comprised of families. The city is also home to the Delaware Valley Job Corps Center, a former seminary. The Delaware Free Library is located on Main Street in the city's business district. The Sullivan County Democrat is a biweekly newspaper with its main office on Main Street. There are many schools in the area, including Jeffersonville Elementary School and Jeffersonville Senior High School.
The city is comprised of 296 residents, including 63 individuals under the age of 20. Of the remaining people, 29 are male and 34 are female. A census from 2000 shows that the population is composed of approximately 286 people. The population includes a diverse range of ethnic groups, with 63 percent of residents being white and 45% being black. The census also lists the percentage of people of each race and racial makeup.
Early settlers in the area included John Ruff and Charles Lutz. These men and women were also influential in the local economy. Many were physicians, who believed that living in the hemlock-woods would cure them of their ailments. In fact, many of these people became successful in their trades after they had finished their formal education. The town's balsamic atmosphere had a beneficial effect on their lungs.
The pioneers of Callicoon wanted to provide the children of the town with a high standard of education. They constructed a "hill of science" near the home of Ross C. Rumsey. The hill was surmounted by a log temple with clay interiors. Judson Laire, a genius who has since moved to Robertsonville, was the presiding genius. He later received a board, but was blackballed by the teachers' association.