A spectrokinetic study of the photophysical and photochemical properties of a series of photochromes bearing thienyl (T(1)), dithienyl (T(2)) and terthienyl (T(3)) groups linked to a naphthopyran in position 3 (sp(3) carbon) or 8 (naphtho moiety) has been carried out. The effect of the number and position of the thienyl groups on the excited state properties of the six compounds in the singlet and triplet manifold has been investigated by stationary and pulsed fluorimetric techniques, laser flash photolysis and kinetic analysis of the colouration/decolouration processes upon continuous irradiation. On increasing the length of the oligothiophene moiety, the contribution of fluorescence to the deactivation processes becomes detectable, while the photocolouration yield decreases. Moreover, only for compounds with T(3) groups was the triplet absorption observed by laser flash photolysis; its decay did not contribute to photocolouration. The competition between physical (fluorescence emission and intersystem crossing) and chemical relaxations markedly affects the behaviour of the compound bearing the T(3) group at the naphtho moiety, which shows the most efficient intersystem crossing and fluorescence emission while does not lead to photoproduction of the coloured open form. A parallel study of the NMR spectra of the compounds bearing one thiophene group allowed two and four photomerocyanine-type photoproducts to be identified for the naphtho-substituted and pyran-substituted compounds, respectively. The compound with a thiophene group at the naphtho moiety was studied in more detail at different temperatures. On the basis of the combined optical and NMR spectrometric results, a reasonable mechanism of its photochromic behaviour is proposed.