The aim of this study was to investigate changes in experimentally recorded M-waves with progressive motor unit (MU) activation induced by transcutaneous electrical stimulation with different pulse waveforms. In 10 subjects, surface electromyographic signals were detected with a linear electrode array during electrically elicited contractions of the biceps brachii muscle. Three different monophasic waveforms of 304-micros duration were applied to the stimulation electrode on the main muscle motor point: triangular, square, and sinusoidal. For each waveform, increasing stimulation current intensities were applied in 10 s (frequency: 20 Hz). It was found that: (a) the degree of MU activation, as indicated by M-wave average rectified value, was a function of the injected charge and not of the stimulation waveform, and (b) MUs tended to be recruited in order of increasing conduction velocity with increasing charge of transcutaneous stimulation. Moreover, the subjects reported lower discomfort during the contractions elicited by the triangular waveform with respect to the others. Since subject tolerance to the stimulation protocol must be considered as important as MU recruitment in determining the effectiveness of neuromuscular electrical stimulation (NMES), we suggest that both charge and waveform of the stimulation pulses should be considered relevant parameters for optimizing NMES protocols.