Particular neuromuscular electrical stimulation (NMES) applications require the use of the same electrodes over a long duration (>1 day) without having access to them. Under such circumstance the quality of the electrode-skin contact cannot be assessed. We used the NMES signal itself to assess the quality of the electrode-skin contact and the electrical properties of the underlying tissues over a week. A 14% decrease in the skin's stratum corneum resistance (from 20 to 17 kΩ) and a 15% decrease in the resistance of the electrodes and underlying tissues (from 550 to 460 Ω) were observed in the 14 healthy subjects investigated. A follow-on investigation of the effect of exercise-induced sweating on the electrical properties of the electrode-skin-underlying tissue composite during NMES indicated a correlation between the decrease in the resistance values observed over the course of the week and the accumulation of sweat at the electrode-skin interface. The value of the capacitance representing the dielectric properties of the skin's stratum corneum increased after exercise-induced sweating but did not change significantly over the course of the week. We conclude that valuable information about the electrode-skin-underlying tissue composite can be gathered using the NMES signal itself, and suggest that this is a practical, safe and relatively simple method for monitoring these electrical properties during long-term stimulation.