Subpicosecond absorption and gain spectroscopy are used to investigate the excited-state behavior of push-pull polyenes made of a diethylthiobarbituric acid electron-acceptor group and a dibutylaniline electron-donor group linked by a pi-conjugated chain. Four polyenes of increasing length, ranging from n = 2 to 5 double bonds, are compared. The relaxation path and relaxation kinetics are studied in dioxane and in cyclohexane, a polar and a nonpolar solvent, respectively. In dioxane, the results provide evidence for the formation of an emissive transient state on an ultrashort time scale (2-3 ps) attributed to a charge transfer (CT) state. The regular shift of the gain peak of this transient state with increase in the chain length (ca. 100 nm per added double bond) indicates that its structure is similar to that of a cyanine, i.e. with a fully conjugated polyenic chain. Its lifetime ranges from a few tens to a few hundreds of picoseconds depending on the chain length. When the number of double bonds increases from n = 2 to 3, the lifetime increases, then decreases continuously for longer chains. In cyclohexane, where the transient CT state is not formed, the decay of the initial excited state follows the same trend when the chain length increases but the lifetimes are shorter than that of the CT state in dioxane. In both solvents, the characterization of long-lived photoproducts by synchronizing two low repetition-rate subpicosecond laser systems demonstrates a change in the relaxation route as the chain length increases. Isomerization occurs for n = 2, whereas intersystem crossing to the triplet state occurs for n = 4. The change in the relaxation channel is observed for n = 3 in both solvents with however a solvent-dependent behavior. In dioxane, relaxation to the triplet state is already observed for n = 3, while an intermediate regime with a relaxation directly to the ground state is observed in cyclohexane. The photophysics of the studied push-pull polyenes is tentatively compared to that of polymethine cyanines and substituted carotenoids.