Thiophene oligomers (nT) with two to six units insolution are studied under pulse excitation (308nm,350fs) in the spectral range 430−830 nm. Transient absorption andinduced fluorescence emerge within 1−2ps. An “instant” absorption (A0), which shows a size dependentspectral structure superimposes the inducedfluorescence during the first 500 fs. The fast kinetic processesof different nT are very similar during thefirst picosecond. They were interpreted as relaxation startingfrom the highest accessible electronic leveldown to the lowest excited-state S1 of eacholigomer.