Résumé : A novel trap mitigation mechanism using molecular additives, which relieves a characteristic early turn‐on voltage in a high‐mobility p‐type acene‐based small‐molecule organic semiconductor, when processed from hydrous solvents, is reported. The early turn‐on voltage is attributed to photo‐induced trapping, and additive incorporation is found to be very effective in suppressing this effect. Remarkably, the molecular additive does not disturb the charge transport properties of the small‐molecule semiconductor, but rather intercalates in the crystal structure. This novel technique allows for the solution‐processing of small molecular semiconductors from hydrous solvents, greatly simplifying manufacturing processes for large‐area electronics. Along with various electric and spectroscopic characterization techniques, simulations have given a deeper insight into the trap mitigation effect induced by the additive.