The ground state conformation, spectroscopy, and photochemical behavior of styrene and eight of its vinyl- and ring-methylated derivatives have been investigated. Introduction of methyl groups at the a-position of the vinyl group or the ortho positions of the phenyl results in increased phenyl-vinyl dihedral angles. Styrenes possessing both a-methyl and ortho-methyl groups adopt orthogonal geometries. Decreased planarity results in a progressive blue-shift in the lowest energy allowed pi,pi* transition and a decrease in the singlet lifetime. Kinetic modeling of the temperature-dependent singlet lifetimes provides activation parameters for the activated decay pathway, which is assigned to C=C torsion for styrenes with phenyl-vinyl dihedral angles, phi, < 60degrees. Planar styrenes have large torsional barriers (7 +/- 1 kcal/mol) and decay predominantly via intersystem crossing and fluorescence at room temperature. Styrenes with values of 30degrees < phi < 60degrees have smaller torsional barriers and decay predominantly via C=C torsion at room temperature. Highly nonplanar styrenes decay predominantly via relatively rapid, weakly activated intersystem crossing.