Background/Objectives: This study aimed to investigate the effects of intrinsic and extrinsic motivation on selective muscle activation of the shoulder girdle during the barbell bench press. Specifically, this research focused on how attentional focus on individual muscles, such as the anterior deltoid (AD), pectoralis major (PM), and triceps brachii long (TBL), could influence their electromyographic (EMG) activity during the exercise. Methods: Twelve male participants, with at least five years of strength training experience, performed bench press exercises under two conditions: with extrinsic motivation (no specific focus on muscle activity) and with intrinsic motivation (internal focus on specific muscles). Surface electromyography (sEMG) was used to measure muscle activity during three sets of bench presses at 60% of one repetition maximum (1RM). Participants were instructed to focus on the activation of specific muscles in a randomized sequence. Results: The intrinsic motivation condition significantly increased muscle activation compared to extrinsic motivation. Electromyographic activity of the AD, PM, and TBL muscles was notably higher when participants focused their attention on these muscles. AD activation increased from 71.78 ± 11.13%MVC (extrinsic) to 88.03 ± 8.84%MVC (intrinsic) (p = 0.0019), while PM and TBL activation also demonstrated significant increases under intrinsic focus. Conclusions: The study concludes that intrinsic motivation, or an internal focus on specific muscle activation, can significantly enhance EMG activity in target muscles during the bench press exercise. This finding has important implications for resistance training and rehabilitation, where focused muscle activation can be utilized to improve training outcomes and muscle engagement.