The objective of this proposal experiment lies in using in situ annealing experiments on a temporal scale to clarify the correlation between the morphology evolution of complex multicomponent organic solar cells (OSCs) and their device performance, which aims to precise control the phase separation length scales through the manipulation of crystallization, and seek to identify the optimal balance between crystallization and phase separation to achieve efficient and stable organic solar cells. Our motivation is to integrate kinetic and thermodynamic analyses to uncover the transformation from single-molecular packing to multiple-phase-scale changes for the morphological evolution during thermal annealing treatment of thin films deposited by ultrasonic spray-coating and to reveal the complex structure-performance relationships that connect morphological evolution with device efficiency.