Information on motor strategies can be extracted from the surface electromyogram (EMG) by non-linear methods. The percentage of determinism (%DET) obtained from recurrence quantification analysis (RQA) may be a sensitive variable to detect synchronous motor unit behaviour. The purpose of the present study was to validate this methodology by comparing it with an established technique estimating the degree of synchronization of pairs of voluntary activated motor units from the correlation of their firing in the time-domain. Single motor unit activity was recorded in extensor carpi radialis (ECR) muscle by pairs of tungsten microelectrodes inserted into the muscle belly. Cross-correlation analysis was performed in order to determine synchronization peak area by computing synchronous impulse probability. Surface EMG activity was recorded in parallel by electrodes placed over the skin of the same muscle and %DET was used as a measure of synchronous activity. The %DET appeared to be a valid measure of synchronization yielding results comparable to those obtained with cross-correlation analysis. Increases in %DET (t = 64.59, P < 0.0001) highly correlated (r2 = 0.70, P = 0.0013) with pharmacologically induced increases in the synchronization activity of pairs of ECR motor units (t = 8.71, P < 0.0001). RQA may be used as an alternative methodology for testing synchronous motor unit behaviour from surface EMG under physiological and pathological conditions.