The preferential use of one leg over another in performing lower-limb motor tasks (i.e., leg dominance) is considered to be one of the internal risk factors for sports-related lower-limb injuries. The current study aimed to investigate the effects of leg dominance on postural control during unipedal balancing on three different support surfaces with increasing levels of instability: a firm surface, a foam pad, and a multiaxial balance board. In addition, the interaction effect between leg dominance and surface stability was also tested. To this end, a tri-axial accelerometer-based smartphone sensor was placed over the lumbar spine (L5) of 22 young adults (21.5 ± 0.6 years) to record postural accelerations. Sample entropy (SampEn) was applied to acceleration data as a measure of postural sway regularity (i.e., postural control complexity). The results show that leg dominance (p < 0.001) and interaction (p < 0.001) effects emerge in all acceleration directions. Specifically, balancing on the dominant (kicking) leg shows more irregular postural acceleration fluctuations (high SampEn), reflecting a higher postural control efficiency or automaticity than balancing on the non-dominant leg. However, the interaction effects suggest that unipedal balancing training on unstable surfaces is recommended to reduce interlimb differences in neuromuscular control for injury prevention and rehabilitation.