Oligothiophenes and polythiophenes are building blocks of organic-based energy conversion materials. Therefore the lifetime of the excited states plays a central role. As a first step to understand the factors influencing the performance, we investigated the deactivation processes from the first excited state S₁ of thiophene and small oligothiophenes containing up to four rings using quantum chemical calculations. For thiophene a low-lying S₁/S₀ conical intersection seam is easily accessible and drives the fast internal conversion. In oligothiophenes barriers inhibit this passage while deactivation pathways via intersystem crossing channels open. The first one is responsible for the high triplet quantum yields and takes place shortly after the Franck–Condon region. The second one occurs in the vicinity of a local S₁ minimum. The calculated spin–orbit coupling strength together with the singlet–triplet energy gaps can explain the decreasing triplet and increasing fluorescence quantum yields for growing chain length. From the triplets the ground state is reachable by inter-ring torsions and T₁/S₀ intersections. The present results allow a deeper understanding of the deactivation pathways of thiophene and small oligothiophenes and are of potential interest for the photophysics of longer oligothiophenes and polythiophenes used in optical devices.