This study aims to expand the artificial lighting potential of controlled environment cultivations systems by introducing UV-A (~315–400 nm) wavelengths into the traditional, visible spectrum lighting, seeking to improve the nutritional and sensory value of cultivated leafy vegetables. The experiment was conducted in a closed climate-controlled chamber, maintaining 21/17 °C day/night temperature, ~55% relative humidity, and a 16 h photo/thermo period. Several genotypes of leafy vegetables, red and green leaf lettuce cultivars, mustard, and kale were cultivated under 250 µmol m−2s−1 basal LED lighting, supplemented by 385 nm UV-A or 405 UV-A/violet wavelengths for 1.1 mW cm−2 for 12 h photoperiod for the whole cultivation cycle. The results show that UV-A/violet light impacts on leafy vegetable growth, free radical scavenging activity, sugar, and phytochemical (α tocopherol, α + β carotenes, epicatechin, rosmarinic and chicoric acid contents) are species-specific, and do not correlate with untrained consumer’s sensory evaluation scores. The 405 nm light is preferable for higher antioxidant and/or sensory properties of kale, mustard, and green leaf lettuces, but both UV-A wavelengths reduce growth parameters in red leaf lettuce.