Background: ActiMotus, a thigh-accelerometer-based software used for the classification of postures and movements (PaMs), has shown high accuracy among adults and school-aged children; however, its accuracy among younger children and potential differences between sexes are unknown. This study aimed to evaluate the accuracy of ActiMotus to measure PaMs among children between 3 and 14 years and to assess if this was influenced by the sex or age of children. Method: Forty-eight children attended a structured ~1-hour data collection session at a laboratory. Thigh acceleration was measured using a SENS accelerometer, which was classified into nine PaMs using the ActiMotus software. Human-coded video recordings of the session provided the ground truth. Results: Based on both F1 scores and balanced accuracy, the highest levels of accuracy were found for lying, sitting, and standing (63.2–88.2%). For walking and running, accuracy measures ranged from 48.0 to 85.8%. The lowest accuracy was observed for classifying stair climbing. We found a higher accuracy for stair climbing among girls compared to boys and for older compared to younger age groups for walking, running, and stair climbing. Conclusions: ActiMotus could accurately detect lying, sitting, and standing among children. The software could be improved for classifying walking, running, and stair climbing, particularly among younger children.