Aim: The aim of this study was to compare the effectiveness of different filling materials and obturation techniques for root canal obturation in primary teeth. Materials and Methods: Eighty maxillary primary incisors were included in this in vitro study. After biomechanical preparation, all samples were scanned using microcomputed tomography (micro-CT) and root canal volumes were calculated. Samples were grouped according to filling materials and obturation techniques, with ten samples in each group. The samples were filled with zinc oxide eugenol (ZOE) and Vitapex using four different obturation techniques (local anesthesia syringe, lentulo spiral, pastinject, and lentulo spiral–ultrasonic activation). After filling, samples were scanned a second time using micro-CT and root canal volumes were calculated. The statistical analysis was performed using SPSS version 24.0. Data were analyzed by Kruskal–Wallis and Mann–Whitney U tests. Results: When the ZOE and Vitapex were compared, it was observed that there were no significant differences between their postobturated volumes, percentage obturated volume (POV), internal void (IV), and percentage of internal void volume (PIV) ( P > .05). The local anesthesia syringe group had a significantly lower postobturated volume and POV, and a significantly higher IV and PIV for both filling materials than that by the other groups ( P < .05). There was no significant difference between the other obturation techniques ( P > .05). For the local anesthesia syringe group, postobturated volume and POV were significantly higher and IV and PIV were significantly lower with Vitapex than with ZOE ( P < .05). There was no significant difference between the other obturation techniques filled either with ZOE or Vitapex ( P > .05). Conclusion: Except for the syringe technique, no difference was observed between the ZOE and Vitapex materials. The syringe technique used in the primary root canal filling was less effective than the other techniques, which had similar efficacy, and in this technique, more effective canal filling was achieved with Vitapex.