It is known that the chronotype potentially mediates the performance and tolerance to work in shifts and that shift rotation is associated with negative effects on psychomotor performance. This study aimed to evaluate the effect of chronotype on psychomotor performance throughout a complete shift rotation schedule. Thirty males working in clockwise rotating shifts from a mining company were evaluated under a real-life condition over the following shift schedule: 2 days of day work, 2 days of evening work and 2 days of night work. The chronotype was determined using the Munich Chronotype Questionnaire adapted for shift workers and the obtained scores were categorized by tertiles (early-type, intermediate-type and late-type). Work performance was evaluated by Psychomotor Vigilance Test (PVT) daily just before shift starts and after shift ends. Sleep duration was evaluated by actigraphy over the whole shift. No isolated effect of the shift or interaction between shift and chronotype was found in the performance variables evaluated. A significant isolated effect of the chronotype showed that the early-type individuals had higher values of pre- and post-work Mean of Reaction Time (MRT) (308.77 ± 10.03 ms and 306.37 ± 8.53 ms, respectively) than the intermediate-type (257.61 ± 6.63 ms and 252.91 ± 5.97 ms, respectively, p < 0.001) and the late-type (273.35 ± 6.96 ms and 262.88 ± 6.05 ms, respectively, p < 0.001). In addition, late individuals presented a greater number of lapses of attention (5.00 ± 0.92; p < 0.05) than early (1.94 ± 0.50, p < 0.05) and intermediate (1.33 ± 0.30, p < 0.001) ones. We concluded that, compared with intermediates, late-type workers had a greater number of lapses of attention on the shift schedule as a whole, while early-type workers showed the highest pre- and post-work MRT. These findings show that the psychomotor performance of rotating shift workers seems to be influenced by the chronotype, but not by the shift rotation.