Background: This study aimed to assess the effectiveness of laser photobiomodulation (PBM) in reducing postoperative pain following single-visit endodontic treatment in children aged 5–9 years. Methods: Forty children aged 5–9 years with acute irreversible pulpitis in deciduous molars requiring single-visit pulpectomy were included in the study. Pulpectomy was performed according to a standard endodontic protocol. The participants were randomly allocated to two groups: group A received laser photobiomodulation using an 810 nm diode laser applied to the periapical area of the treated tooth postoperatively, and group B received blue light LED, applied at similar points to the control teeth. This was a placebo intervention. Pain scores were measured using a 10-point Visual Analog Scale (VAS) at 4, 12, 24, and 48 h post-treatment. The Friedman test was used to compare the VAS scores within groups over time, and the Mann–Whitney U-test was used to compare the VAS scores between the two groups. The significance level was fixed at p < 0.05. Result: The mean VAS scores were significantly lower in the PBM group compared to the placebo group at the 4th h, 12th h, and 24th h post-treatment (p ≤ 0.05). The pain levels remained stable over time in the PBM group, with no significant difference in pain scores from 4 h to 48 h (p = 0.57). In the placebo group, the pain gradually decreased from the 4th h to the 48th h, with a significant reduction in pain observed between the 12th h and 48th h (p = 0.05). Conclusions: Laser photobiomodulation (PBM) was found to be effective in reducing postoperative pain following single-visit endodontic treatment in children. This non-invasive approach could offer a valuable alternative for pain management in pediatric endodontics, particularly given its effectiveness without the need for systemic medications.