This study aimed to evaluate the effects of preceding anodal transcranial direct stimulation (a-tDCS) over the dorsolateral prefrontal cortex (DLPFC) during the back squat exercise on movement velocity and surface electromyographic (sEMG) activity. Thirteen healthy, well-trained, male firefighters (34.72 ± 3.33 years; 178 ± 7.61 cm; 76.85 ± 11.21 kg; 26.8 ± 4.2 kg·m−2; back squat 1-repetition maximum 141.5 ± 16.3 kg) completed this randomised double-blinded sham-controlled crossover study. After familiarisation and basal measurements, participants attended the laboratory on two occasions separated by 72 h to receive either Sham or a-tDCS (current intensity of 2 mA for 20 min). Immediately after stimulation, participants completed three sets of 12 repetitions (70% of 1-RM) with three minutes of recovery between sets monitored with a linear position transducer. The sEMG of the rectus femoris (RF) and vastus lateralis (VL) of both legs were recorded. No significant differences were observed between a-tDCS and Sham interventions on mean concentric velocity at any set (p > 0.05). Velocity loss and effort index were significantly higher (p < 0.05) in set 3 compared to set 1 only in the a-tDCS group. The right-leg RM and right-leg VL elicited the greatest muscle activation during set 1 after a-tDCS and Sham, respectively (p < 0.05). Our results revealed that a-tDCS over the DLPFC might impact movement velocity or fatigue tolerance in well-trained individuals. Notwithstanding, significant differences in dominant-leg muscle activity were found both in a-tDCS and Sham.