Semiconductor polymers are the foundation of organic electronics due to their remarkable optical features, ability to form a thin film, and low cost compared to silicon. However, some of them have intense photobleaching under UV-blue radiation, compromising several applications. In this context, we have investigated the conformational disorder effect on the real-time photobleaching kinetics of a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)/chloroform solution under deep-blue radiation. Our results pointed out that a 405 nm diode laser initially causes a significant conformational disorder in the π-conjugated backbone of MEH-PPV as revealed by the Huang-Rhys factor. As a result, a new vibrational mode arises with an energy separation of 230 meV, indicating the substitution of the vinyl (C═C) by carbonyl (C═O) bonds. Then, the conformational disorder reaches a maximum value at some tens of minutes, which is inversely proportional to the polymer concentration, and after that, a random chain scission occurs. Consequently, the effective conjugation length of MEH-PPV in chloroform decreases from nine to three coplanar repetitive units after 1 h of excitation, producing a drastic drop in photoluminescence. Finally, we show that the photobleaching steps are mapped through the conformational disorder.