In photo-electrochemical etching for macroporous silicon, the electrolyte diffusion in the macropore greatly influences the formation of macroporous silicon, especially the etching rate and macropore diameter. In this study, the electrolyte diffusion was investigated systematically. We focused on the establishment of the electrolyte diffusion model and its impact on the etching rate and macropore diameter. By solving the diffusion equation, the electrolyte diffusion model was deduced, which is different from the commonly accepted model. The main difference is that, in the model, the HF concentration at the macropore tip decreases nonlinearly with macropore length. The module can effectively predict the etching rate. Based on this model, the practical method of etching current density adjustment for fabricating high aspect ratio macroporous silicon was proposed. In addition, the samples were fabricated with a constant etching current density and corrected etching current density. The experimental result indicates that the novel electrolyte diffusion model is practical. The finding from this study shows that the adjustment of etching current density based on the electrolyte diffusion model can effectively control the macropore diameter of high aspect ratio macroporous silicon.