Perovskites have attracted great interest in optoelectronics and photonics. As a new class of perovskites, metal-free perovskites have drawn growing attention due to the absence of toxic metal elements in them and their wide chemical diversity. Taking MDABCO-NHI (MDBACO = -methyl-'-diazabicyclo[2.2.2]octonium) and MDABCO-NHBr as examples, our first-principles calculations discover two fundamental features of metal-free perovskites that should be crucial for their applications. First, their photoluminescence emission originates from halogen vacancies, instead of the self-trapped exciton generally suggested. Second, in the vicinity of a halogen vacancy, optical excitation from the valence bands to the empty defect bands may cause release of H and NH molecules, which will not only lead to degradation of the perovskite but also quench its photoluminescence. To prevent the degradation and protect the optoelectronic and photonic performances of metal-free perovskites, short-wavelength illumination needs to be shielded.