The surface photochemistry of trivinylantimony adsorbed on a cold quartz surface was investigated using pulsed 193 nm excimer-laser radiation. The major desorption products observed were C2H2, C2H3, C2H4, C4H6, Sb, Sb(C2H3), Sb(C2H3)2, Sb(C2H3)3 and Sb2. Photoproduct distributions and their Maxwell-Boltzmann characteristic temperatures were determined using time-of-flight mass spectrometry, incorporating both electron impact and, for Sb detection, resonance-enhanced multiphoton ionization. Photoproduct yields and Maxwell-Boltzmann temperatures were dependent on photon fluence, sample dosage and surface temperature. The Maxwell-Boltzmann temperatures of the CxHy, products were substantially lower than those of the metallic and organometallic species, indicating that the desorption of the Sb-containing products probably occurs via electronically excited states. A mechanism is given for the photochemistry of adsorbed trivinylantimony.