The isomerization and cyclization photoreactions of the cis (Z) isomers of n-styrylnaphthalenes (n = 1 and 2), n-styrylphenanthrenes (n = 1, 2, 3, 4, and 9), and two related compounds, 3-styrylchrysene and 3-styrylbenzo[c]phenanthrene, were investigated by spectrophotometric and chromatographic techniques. The quantum yields of the two photoreactions were measured in aerated and deaerated nonpolar solvent at room temperature and compared with those reported in the literature for some of the molecules investigated and other related compounds. The combined use of high-performance liquid chromatographic and spectrophotometric techniques made easier the separation of the components of the photoreaction mixtures thus simplifying the study of the isomerization/cyclization competition and the measurement of the UV-vis absorption spectra and the thermal decay kinetics of the dihydrophenanthrene-type intermediates. The conformational equilibria in the ground state and the positional isomerism (n values) notably affect the prevalence of one or the other competitive photoreaction. Oxygen also plays an important role: practically it does not affect the quantum yield of the Z -> E process but has a drastic effect on the formation of the final oxidation product which call proceed even in the presence of traces of air. In three cases, non-negligible formation of a side colorless product was detected. It was assigned to an isomer of the normal photocyclization intermediate (4a,4b-dihydrophenanthrene-type), formed by shift of one or both hydrogen atom(s) to other positions of the rings. Parallel ab initio calculations of the potential energy of the possible conformers helped to explain the Structure effects on the competitive photoreactive relaxation pathways. Some correlations between the Computed reagent/product energy difference in the ground state and the photocyclization yield and thermal stability of the intermediates were also verified.