A novel approach is proposed for combining phosphor materials with triboelectric nanogenerators (TENGs) for mechanical energy harvesting and illumination applications. For this purpose, strongly reddish‐orange‐emitting Ba0.5Sr0.5Nb2O6:0.25 mol Eu3+ (BSNb:0.25Eu) phosphor materials are synthesized. The photoluminescence properties of the synthesized BSNb:0.25Eu are analyzed. The synthesized BSNb:0.25Eu is utilized as a dielectric filler inside a polydimethylsiloxane polymeric film due to its high dielectric properties to improve the overall dielectric properties of the composite film (CF). TENG devices are fabricated using phosphor‐loaded CFs as the tribonegative layer, transparent polyvinyl alcohol as the tribopositive layer, and aluminum as the conductive electrode. All the TENGs operate in a contact‐separation mode, and the highest electrical output is attained by optimizing the phosphor filler concentration in the CF. The optimized TENG exhibits excellent stability in long‐term operational tests, under varying harsh ambient temperatures. Indium tin oxide sputtered on both triboelectric films as an electrode and combined with a transparent hard substrate to obtain a fully transparent TENG. A self‐illuminating TENG (SI‐TENG) is fabricated by integrating near‐ultraviolet light‐emitting diodes between two identical TENGs. The SI‐TENG can harvest the mechanical energy available in the surrounding environment and illuminate it as a light source. Additionally, the proposed phosphor‐loaded polymer films can be employed for optical thermometry and mechanical energy harvesting via SI‐TENG on a large scale.