The special grand jury was investigating adults knew of the rape allegation but failed to report it as required by state law. The West Virginia girl had been raped after an alcohol-fueled party in August 2012 following a team scrimmage, and there were allegations of a cover-up in the eastern Ohio mining community.
In March, 17-year-old Ma'Lik Richmond was convicted of rape and sentenced to a year in the juvenile prison system. Trent Mays, also 17, was convicted of rape and of using his phone to take a picture of the girl naked and sentenced to two years in juvenile detention.
Ohio Attorney General Mike DeWine said the case initially was about the teenagers, but it had become just as much about the adults, including the parents.
"How do you hold kids accountable if you don't hold the adults accountable?" he said.
The charges against the Superintendent Mike McVey include felony counts of obstructing justice.
Lynnett Gorman, an elementary school principal, and Seth Fluharty, a strength coach at Steubenville High School, are charged with failing to report possible child abuse. A former volunteer coach, Matthew Belerdine, faces several misdemeanor charges, including making false statements and contributing to underage alcohol consumption.
The four adults are scheduled to appear in Jefferson County Common Pleas Court on Dec. 6. They have not yet entered a plea.
The grand jury earlier charged the Steubenville schools' information technology director with tampering with evidence, obstructing justice, obstructing official business and perjury. The panel also indicted that man's daughter on theft and receiving stolen property charges unrelated to the rape case. Both have pleaded not guilty.
ABC News and The Associated Press contributed to this report.