The steady growth of end-of-life (EoL) crystalline silicon (c-Si) photovoltaic (PV) modules requires the development of recycling technologies to guarantee sustainable circular development for the environment. Therefore, we use cyanogenic bioleaching to recover valuable metals from c-Si PV cells. The kinetic mechanism of the leaching process was evaluated. In addition, the complexation of cyanide on the metal surface was further explored from the perspective of adsorption models. The experimental data show that bioleaching can effectively recover Ag and Al, and the leaching process is controlled by chemical reaction and diffusion. On the metal surface, the C-terminal adsorption of CN– is more advantageous than the N-terminal vertical adsorption. CN– is prone to mutual isomerization between the more stable configurations on the metal surface, and rotation is prone to occur between the adsorption configurations. The results of the charge density difference showed that when CN– was adsorbed on the metal surface, the charge was transferred from the metal surface to the cyanide radical, and the electrons were mainly obtained by C, while N lost part of the electrons. Hence, the results of this study confirm that the culture of Pseudomonas fluorescens can recover metals from retired c-Si PV cells