Objective The aim of this study was to evaluate and compare, both clinically and radiographically, the effects of calcium silicate-based materials (i.e., ProRoot MTA [PR-MTA], MTA-Plus [MTA-P], and Biodentine [BD]) and ferric sulfate [FS] in pulpotomy of primary molars. Materials and Methods In this randomized clinical trial, 29 healthy 5- to 7-year-old children with at least four carious primary molars with no clinical or radiographic evidence of pulp degeneration were enrolled. The pulpotomy agents were assigned as follows: Group 1: BD; Group 2: MTA-P; Group 3: PR-MTA; and Group 4: FS. Clinical and radiographic evaluations were performed at 6, 12, and 24 months. Data were analyzed using chi-square tests. Results Total success rates at 24 months were 82.75%, 86.2%, 93.1%, and 75.86%, respectively. No statistically significant differences in total success rates were observed among the groups at 6-, 12-, and 24-month follow-ups. When the groups were compared according to follow-up times, the success rates in each group did not vary significantly among the 6–12-month, 6–24-month, or 12–24-month periods (p > 0.05). Conclusion Although the success rates of BD, MTA-P, MTA-PR, and FS did not differ significantly, calcium silicate-based materials appeared to be more appropriate than FS in clinical practice.