Abstract: OH (hydroxyl radical) is a key reactive component in Earth's atmosphere and interstellar media. In this work, we calculated the doublet electronic states of the OH using the MRCI method. Compared with previous studies, both the computational accuracy and the number of electronic states have been significantly improved, and the obtained spectroscopic constants are in good agreement with experimental data. In view of the significant avoided crossings between the potential energy curves of the ²Π electronic states, we investigated the non-adiabatic coupling in the photodissociation process. By calculating the radial coupling matrix elements, strong non-adiabatic interactions between the ²Π electronic states were revealed. Based on these results, we solved the coupled nuclear Schrödinger equation and obtained photodissociation cross sections exhibiting a series of resonant peaks caused by Feshbach resonances. The positions of these peaks closely match the bound energy levels in the non-adiabatic representation. The high-precision electronic structure data and the related photodissociation dynamics mechanisms provided in this study are of significant value for a deeper understanding of atmospheric material transformation processes and interstellar chemical reactions.