This paper aims to fabricate high aspect ratio through silicon via (TSV) by photo-assisted electrochemical etching (PAECE) and supercritical copper electroplating. A blind-holed silicon array was first fabricated by PAECE. By studying the etching parameters, including hydrofluoric acid concentration, etchant temperature, stirring speed, tetrabutylammonium perchlorate (TBAP) content, and Ohmic contact thickness, an array of pores with a aspect ratio ( and ) was obtained successfully. Moreover, TBAP and Kodak Photo-Flo (PF) solution were added into the etchant to acquire smooth sidewalls for the first time. TBAP was added for the first time to serve as an antistatic agent in deionized water-based etchant to prevent side-branch etching, and PF was used to degasify hydrogen bubbles in the etchant. The effect of gold thickness over Ohmic contact was investigated. Randomized etching was observed with an Au thickness of 200 Å, but it can be improved by increasing the etching voltage. The silicon mold of through-holes was filled with metal using supercritical copper electroplating, which features high diffusivity, permeability, and density. The TSV structure (aspect ) was obtained at a supercritical pressure of 2000 psi, temperature of 50°C, and current density of in 2.5 h.