The photochemical formation of o-xylylene is studied by two-pulse fluorescence and transient absorption spectroscopy. o-Xylylene is produced by photolysis of alpha,alpha’-dichloro-o-xylene, alpha,alpha’-dibromo-o-xylene, alpha,alpha’-bis(trimethylstannyl)-o-xylene, and 2-indanone at 266 nm in room-temperature cyclohexane solution. On excitation at 308 nm, the fluorescence of o-xylylene is observed with a maximum at 460 nm and a lifetime of 9.3 +/- 0.5 ns. The absorption of o-xylylene is obtained with a maximum at 370 nm. The formation of o-xylylene from alpha,alpha’-dichloro-o-xylene occurs, by 266-nm two-photon excitation, with an apparent yield of 0.30 +/- 0.08 at a fluence of 40 mi cm(-2). Its formation from 2-indanone proceeds, by 266-nm one-photon excitation, with a rate of (1.4 +/- 0.1) x 10(7) s(-1) and a yield of 0.90 +/- 0.08.