The photophysical and photochemical properties of four 3,3-diphenyl-3H-naphtho[2,1-b]pyrans substituted, via an acetylenic junction, to (thiophene)(n) oligomers (n = 0-3 units) were investigated by transient absorption in the femtosecond to microsecond time domain and by stationary absorption and fluorescence. The decay of the initially produced excited S-1(pi pi*) state is found to occur via three competing processes: fluorescence, intersystem crossing, and a ring-opening reaction leading to a colored merocyanine product, with relative yields varying drastically with n. Whereas ultralast (sub-picosecond) reaction dynamics and high product quantum yield are observed for n = 0 and 1, the reaction is considerably slowed down on going to the n = 2 (105 ps) compound and does not occur for n = 3. A reaction scheme that accounts for this behavior is proposed and the effect of the oligothiophenic chain length on the photoinduced properties is discussed. It is suggested that increasing the chain length from 1 to 3 thiophene units stabilizes the S-1(pi pi*) state by pi conjugation and induces an excited-state potential barrier along the reaction pathway.