The effects of the different electrical frequencies of whole-body electrical stimulation (WB-EMS) on energy expenditure (EE) and the respiratory exchange ratio (RER) remain poorly understood. This study aimed to determine the effects of different WB-EMS electrical frequencies on EE and the RER during supine resting and uphill walking. A total of 10 healthy and recreationally active men (21.6 ± 3.3 years old) participated in the present study. Participants completed two testing sessions in a randomized order. In each session, a variety of impulse frequencies (1 hertz (Hz), 2 Hz, 4 Hz, 6 Hz, 8 Hz, and 10 Hz) were applied in a randomized order, allowing a 10 min passive recovery between them. Oxygen consumption and carbon dioxide production were measured to calculate EE and the RER. All frequencies increased EE at rest (all p ≤ 0.001), with 4 Hz being the frequency producing the highest increase (Δ = 8.89 ± 1.49 kcal/min), as did 6 Hz (Δ = 8.05 ± 1.52 kcal/min) and 8 Hz (Δ = 7.04 ± 2.16 kcal/min). An increment in the RER at rest was observed with 4 Hz, 6 Hz, 8 Hz and 10 Hz (all p ≤ 0.016), but not with 1 Hz and 2 Hz (p ≥ 0.923). During uphill walking, the frequency that elicited the highest increase in EE was 6 Hz (Δ = 4.87 ± 0.84 kcal/min) compared to the unstimulated condition. None of the impulse frequencies altered the RER during uphill walking. WB-EMS increases EE in healthy young men both during resting and uphill walking.