This study attempts to analyze the relationship between free-throw efficiency and the time of arm muscle activation in players from 3 basketball teams with different levels of experience was investigated. During the experiment each player made 20 free throws during which the activation time of his right and left biceps and triceps brachii muscles were measured with the use of surface electromyography and high-speed cameras. Significant differences in muscle activation time (t) during a free throw were found between the groups of basketball players (p = 0.038) (novices: t = 0.664 ± 0.225 s, intermediate-level players: t = 1.15 ± 0.146 s, experts: t = 1.01 ± 0.388 s). In the right triceps brachii muscle in expert basketball players the coefficient of variation (CV) amounted to 44.60% at 81% efficiency, and in novices to 27.12% at 53% efficiency. The time of arm muscle activation during a free throw and its fluctuations vary along with the training experience of basketball players. In all studied groups of players, the variability of muscle activation time in accurate free throws is greater than in inaccurate free throws. Free-throw speed is irrelevant for free-throw efficiency.