Postural balance is a key element of shooting effectiveness, which determines the outcome of modern pentathlon competitions. The aim of the study is to examine the postural balance of 27 pentathletes (12 females and 15 males; mean age: 18.0 ± 1.8 years), and 26 physically active, untrained subjects (12 females and 14 males; mean age: 22.5 ± 1.4 years), and to investigate the impact of footwear on the stability of the shooting position in pentathletes. Methods: Static postural balance was examined during quiet stance in four test conditions (standing in footwear with eyes opened, standing in footwear with eyes closed, standing barefoot with eyes opened, and standing barefoot with eyes closed). During each postural balance measurement, the participant remained still on the platform, with their arms in front of their body. Postural balance in the shooting position was only evaluated in the group of pentathletes. The athlete was asked to assume a comfortable shooting position on the platform and to aim at the target. Standard pentathlon targets and pistols were used in the study. Measurements were carried out twice (barefoot and in footwear). Results: In all conditions, pentathletes achieved lower values of posturographic measures than in the control group. In non-visual conditions, measures describing the surface area of the centre of pressure decreased in pentathletes and increased in the control group. Both pentathletes and non-athletes were equally stable barefoot as in footwear. Footwear did not affect postural sway in the shooting position in pentathletes. Conclusions: Pentathletes were found to have significantly better stance stability and were less vision-dependent in postural balance than untrained subjects. Bearing in mind that the shooting position of pentathletes was as stable barefoot as in footwear, the main factors which were most likely responsible for minimising body oscillations in the pentathletes were their high level of concentration and conscious control of body alignment.