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Abstract Violet phosphorus (VP) is garnering attention for its appealing physical properties and potential applications in optoelectronics. A comprehensive investigation of the photodegradation and thermal effects of exfoliated VP on SiO₂/Si substrates is presented. The degradation rate of VP is strongly influenced by the wavelength and exposure duration of light. Light illumination of VP above the bandgap leads to faster degradation, attributed to interactions with reactive oxygen species. Power‐dependent photoluminescence (PL) measurements at low temperature (T = 4 K) show neutral exciton (X⁰) and trion (T) intensities linearly increase with excitation power, while the energy difference between peak energies decreases. The T/X⁰spectral weight ratio increases from 0.28 at 300 K to 0.69 at 4 K, suggesting enhanced T formation due to reduced phonon scattering. Temperature‐dependent Raman is used to investigate the phonon properties of VP. Tracking peak positions of 9 Raman modes with temperature, the linear first‐order temperature coefficient is obtained and found to be linear for all modes. The results provide a deeper understanding of VP's degradation behavior and implications for optoelectronic applications.