The unusually intense luminescence (commonly called triboluminescence) observed when opening self-seal envelopes has been studied using spectroscopy. Emissions from gas-phase species due to electrical discharge were observed, which in the case of air consists of vibronic transitions of N-2(C-3 Pi(u)-B-3 Pi(g)) in the ultraviolet (UV) region (280-400 nm). However, the major cause of the intense blue luminescence (around 435 nm) is attributed to optical brightening agents added to the white paper. The results suggest that the emission from the brightening agents may be caused by two mechanisms: (i) fluorescence due to excitation by the UV light from the gas discharge and (ii) nonoptically, by electron transfer. The electrical discharge results from contact electrification; we propose a mechanism for the charge transfer involving a net migration of hydroxide anions out of the paper into the wet latex-adhesive during drying.