The aim of this study was to compare soccer goalkeepers’ decision-making times following a shot on goal and to determine goalkeepers’ movement pattern structures using EMG in a typical game situation (two-on-one). Two groups of goalkeepers (n = 60) took part in the study: Group A, the senior group (22.00 ± 2.35 years of age), and Group B, the youth group (15.38 ± 1.32 years of age). The goalkeepers’ decision-making times were measured by using EMG from the moment the attacker struck the ball until the completion of the saving action by the goalkeeper. Subsequently, the goalkeepers’ movement pattern structure was determined (for both Groups A and B), and the values of muscle bioelectrical tension during a typical defensive situation in training conditions were revealed. The findings clearly indicate a significantly (p = 0.001) shorter decision-making time in experienced goalkeepers (250–260 ms) than in novices (300–320 ms). In addition, the movement pattern structure confirmed the hypotheses on the economization of effort and the visual-muscular coordination of the postural muscles (calf muscles) that affect soccer goalkeepers. The study also demonstrated a lower bioelectric tension of the gastrocnemius muscle (GAS.MED. RT—p = 0.008; GAS.LAT. RT—p = 0.030) in the expert goalkeepers.