The move comes just three days after Tennessee parted ways with defensive coordinator John Jancek.
"We are very excited about the addition of Bob Shoop to our coaching staff," Volunteers coach Butch Jones said in a statement. "Bob has established himself as one of the premier coordinators in all of college football and is very well-respected as a recruiter, football coach and person. He brings a wealth of experience at the highest level and possesses all the qualities we were looking for as we went through this process."
At Penn State, Shoop inherited a mediocre defense that ranked No. 48 in yards allowed in 2013. In 2014, Shoop vaulted that defense to the No. 2 ranking in total defense and, despite several key departures, ranked No. 14 this past season.
The Nittany Lions announced that co-defensive coordinator and assistant head coach Brent Pry, who oversaw the linebackers, will replace Shoop as associate head coach and defensive coordinator. Terry Smith will be the assistant head coach while keeping the title of defensive recruiting coordinator and cornerbacks coach.
Shoop boasts 27 years of experience, including three years as Vanderbilt's defensive coordinator. In his last season in the SEC, Shoop's Commodores upset Tennessee by limiting the Vols' offense to just 10 points.
"This was not an easy decision and one that I didn't take lightly," Shoop said in a statement. "Over the last 24 hours I had an opportunity [to] meet with Coach Jones and his staff. It became evident to me that he is building a great program, a program on the rise and certainly one that will compete for an SEC Championship. I'm looking forward to becoming a part of the team."
Shoop takes over a Tennessee defense that finished No. 36 nationally in total defense and No. 16 nationally in scoring defense. However, in three of the Volunteers' four losses, the defense failed to hold a double-digit lead.
Shoop's departure may come as a bit of a surprise in Happy Valley. On Dec. 29, prior to the TaxSlayer Bowl, Shoop told a group of reporters he planned on staying at Penn State.
"I don't plan on going anywhere," he said.