Hollin Pierce attended Trenton High School in New Jersey and played the offensive and defensive lines for coach Greg Hyslop. The 6-foot-8 athlete also was a member of the varsity basketball team at Trenton. After high school. Pierce played one postgraduate season in 2019 at Fork Union military Academy (Va.) but was not offered any division one offers and decided to walk on at Rutgers University.
As a freshman in 2020, Pierce played in one game. He made his collegiate debut on the field goal protection but broke through in 2021 and became the Scarlet Knights starting right tackle. He played in all 13 games with 12 starts and earned the Mark Mills Second Effort Award as the most improved offensive player during spring practice. In 2022, he started all 12 games at right tackle and was named a candidate for the Burlsworth Trophy, which honors the most outstanding football player who began his career as a walk-on and has shown outstanding performance on the field.
Pierce switched over to left tackle and started all 13 games for the Scarlet Knights where he was part of a unit that led the Big Ten in fewest sacks allowed per game (1.08) and ranked fifth in the league in rushing (168.7). After the season was completed, Pierce was voted honorable mention All-Big Ten.