Electrochemical anodization provides the scalability required for structuring porous silicon (PSi) layers for mass production; hence, new and feasible processes are highly sought-after. We investigate the effect of surfactant (additive) and etching time on the morphology of PSi matrix in a simplistic two-electrode anodization cell using aqueous HF electrolyte. Instead of the conventional galvanostatic mode (constant current density), we use the rarely reported technique of potentiostatic anodization (constant applied potential) for engineering PSi surface morphology. We demonstrate that under a constant applied potential, channel-like morphology, pyramids or well-ordered macropores are easily achieved through either increasing the processing time or adding a small amount of surfactant into the electrolyte. Our results provide better understanding of the mechanism underlying the formation of PSi and propose a practical solution for obtaining application-specific macrostructure of PSi.