This study characterized the level of oxidative metabolism in skeletal muscle during whole-body activity as a percentage of the muscle’s maximum oxidative rate (mVO2max) using near-infrared spectroscopy (NIRS). Ten healthy participants completed a progressive work test and whole-body walking and lunge exercises, while oxygen saturation was collected from the vastus lateralis muscle using near-infrared spectroscopy (NIRS). Muscle oxygen consumption (mVO2) was determined using arterial occlusions following each exercise. mVO2max was extrapolated from the mVO2 values determined from the progressive exercise test. mVO2max was 11.3 ± 3.3%/s on day one and 12.0 ± 2.9%/s on day two (p = 0.07). mVO2max had similar variation (ICC = 0.95, CV = 6.4%) to NIRS measures of oxidative metabolism. There was a progressive increase in mVO2 with walking at 3.2 Km/h, 4.8 km/h, 6.4 Km/h, and with lunges (15.8 ± 6.6%, 20.5 ± 7.2%, 26.0 ± 6.6%, and 57.4 ± 15.4% of mVO2max, respectively). Lunges showed a high reliability (ICC = 0.81, CV = 10.2%). Muscle oxidative metabolism in response to whole-body exercise can be reproducibly measured with arterial occlusions and NIRS. This method may be used to further research on mitochondrial activation within a single muscle during whole-body exercise.