The correlation between morphology and optoelectronic performance in organic thin‐film transistors based on blends of photochromic diarylethenes (DAE) and poly(3‐hexylthiophene) (P3HT) is investigated by varying molecular weight (Mw = 20–100 kDa) and regioregularity of the conjugated polymer as well as the temperature of thermal annealing (rt‐160 °C) in thin films. Semicrystalline architectures of P3HT/DAE blends comprise crystalline domains, ensuring efficient charge transport, and less aggregated regions, where DAEs are located as a result of their spontaneous expulsion from the crystalline domains during the self‐assembly. The best compromise between field‐effect mobility (μ) and switching capabilities is observed in blends containing P3HT with Mw = 50 kDa, exhibiting μ as high as 1 × 10−3 cm2 V−1 s−1 combined with a >50% photoswitching ratio. Higher or lower Mw than 50 kDa are found to be …