Objective: To evaluate the influence of four different photoinitiators on the polymerization kinetics and marginal microleakage in class V restorations using photopolymerizable dental composites. Material and Methods: Four photopolymerizable dental composites based on Bis-GMA (14.5 wt %), UDMA (6.5 wt %) and silanized filler particles (79 wt %) containing different photoinitiators were formulated. Camphorquinone (CQ)/amine, phenyl-propanedione (PPD), monoacylphosphine oxide (Lucirin ® TPO) and bisacylphosphine oxide (Irgacure ® 819) were used as photoinitiators. Sixteen intact human third molars were selected and divided into four groups. All teeth received class V cavity preparations in their buccal and lingual surfaces and were submitted to a dye leakage test. Data were independently analyzed for both enamel and dentin, and the results were assessed by a Kruskal-Walis test. The polymerization reactions of the four composites were evaluated by differential scanning calorimeter coupled with photocalorimeter accessory. Results: Lucirin ® TPO presented the highest scores for microleakage in enamel, whereas the other photoinitiators have not demonstrated statistical differences. The lowest scores were obtained for PPD in dentin while the highest scores have been achieved by Irgacure ® 819 and Lucirin ® TPO. Photocalorimetric measurements demonstrated a correlation between polymerization reaction rate and marginal leakage, showing that faster reactions cause greater marginal leakage. Conclusion: Marginal microleakage scores in photopolymerizable dental composites can be greatly influenced by different types of photoinitiators through their distinct reaction rates.