The aim of this study was to investigate how the rating of perceived exertion (RPE) during resistance exercises was influenced by the exercise volume and athletes' training state. Eighty physical education students (well trained, less well trained, and novices) rated their perceived exertion of multilift sets using the category-ratio scale. These sets were performed with moderate (60-80% of 1-repetition maximum [1RM]) and heavy loads (80-100% of 1RM) involving low volume of exercise (5.5 ± 1.1 reps for moderate and 1.3 ± 0.4 reps for the heavy load) and high volume of exercise (moderate load: 17.5 ± 2.1 reps; high load: 2.9 ± 0.6 reps). The exercise volume of the sets was expressed relatively to individual maximal capacities using the maximum number of repetition (MNR) for the load lifted. General linear model describes that RPE was related to MNR % with a training state effect (p < 0.01) observed only for sets involving a low MNR % and without effect of absolute volume and exercise intensity (high MNR sets: adjusted R = 0.65 and 0.78 and low MNR sets adjusted R = 0.37 and 0.34 in low MNR tests). High standard errors of estimated relative volume appeared when using the RPE from low exercise volume sets (12.8 and 14.4% of actual relative volume). Coaches should consider the RPE resulting from high exercise-induced physical strain to estimate the actual relative volume and to estimate the individual MNR at a given load.