The Volunteers, who had climbed as high as No. 7 in the polls after wins over Villanova and Pittsburgh, lost their third nonconference home game in December, only the fifth such loss in coach Bruce Pearl's six seasons.
Since the Dec. 11 win against then-No. 3 Pittsburgh, the Vols have lost to Oakland, Charlotte and Southern California and narrowly beat Belmont and Tennesse-Martin.
It's not the first win for College of Charleston against Tennessee. The Cougars beat the Vols 55-49 in Knoxville on March 13, 1996, knocking Tennessee out of the first round of the NIT. The Vols won their previous meeting 86-69 on Nov. 27, 2009.
After Willis Hall had an air ball 3-point shot to open the game, the senior-laden College of Charleston (9-4) hit its next seven shots, including three 3s from Antwaine Wiggins and two 3s by Goudelock. The Cougars never trailed after that.
Another 3-pointer by Goudelock with 9:02 in the first half pushed the lead to 35-13, the largest of the game for the Cougars, who were 7 of 11 from 3-point range and shot 55.2 percent in the first half. They finished 14 of 25 from long range.
Antwaine Wiggins added 15 points for the Cougars, and Jeremy Simmons had 11.
Goudelock's third 3-pointer seemed to shake Tennessee from its slump, and the Vols answered with a 15-2 run by fighting to get inside to the basket more. A pair of Hopson free throws made it 37-30 with 5:15 left in the first half, and College of Charleston entered halftime with a 47-40 lead.
The Vols (9-4) hung close for a few minutes until back-to-back 3s gave the Cougars a 70-53 lead with 11:58 to go. Tennessee began to get called for fouls as players got more frustrated, and College of Charleston hit 21 of 34 at the foul line.
Pearl got increasingly frustrated with the disparity in the number of fouls called by the officials and was given a technical foul after Josh Bone fouled Monroe with 5:25 to go. Pearl continued to argue from the sideline as Goudelock hit two free throws, and officials called another technical on the coach, leading to his ejection.
"I was just trying to get Tony Jones some reps, that's all," Pearl said, referencing the associate head coach who will take over for him during his suspension. "I wasn't talking to the official when I was ejected, so that's what I was surprised about."
It was the third ejection in Pearl's career, the previous two coming during his coaching stints at Wisconsin-Milwaukee and Southern Indiana.
Pearl has just one more game, a Jan. 5 meeting at home against Memphis (No. 22 ESPN/USA Today, No. 21 AP) , before he begins serving an eight-game suspension during Southeastern Conference play. SEC commissioner Mike Slive suspended Pearl for lying to NCAA investigators during an ongoing probe into recruiting practices by the Tennessee coaching staff, and Pearl will miss conference games played between Jan. 8 and Feb. 8.
Tennessee, which outrebounded College of Charleston 47-35, pulled within 10 on a 3 by Bone with 1:32 to go, but it was too little, too late.
Information from The Associated Press was used in this report.