Dynamic motor skills such as volleyball blocking rely on efficient perception–action coupling and are influenced by individual, environmental, and task constraints. However, limited research studies have assessed the effect of an individual constraint such as blocking skill on visual attention during an in-situ volleyball blocking task. Therefore, this study used a cross-sectional, observational design to investigate the gaze behavior of 18 male volleyball players (25.6 ± 4.9 years), of two different levels of blocking skill determined a priori according to success during an on-court blocking task. When compared to relatively unsuccessful players (RUS), the gaze of relatively successful players (RS) was observed to fixate more often (RUS: 0.7 ± 0.7 n, RS: 1.3 ± 0.3 n) and dwell for longer (Total; RUS: 12.2 ± 18.4%, RS: 48.0 ± 37.2%, Phase 4; RUS: 6.6 ± 8.8%, RS: 16.9 ± 12.4%) on the opposition spiker, demonstrating that important perceptual information about an opposing team’s attack lies within the behavior of the opposition spiker. More successful blockers were also observed to be taller (RUS: 181.8 ± 6.6 cm, RS: 192.6 ± 3.9 cm), longer in arm-span (RUS: 185.7 ± 5.6 cm, RS: 195.2 ± 5.6 cm), and heavier (RUS: 78.6 ± 11.4 kg, RS: 90.5 ± 8.5 kg). These results can consequently be used to develop a profile of the visual attention and physical attributes of successful blockers for use in developing talented players.