A highly transparent and efficient counter electrode was facilely fabricated using SiO2/poly­(3,4-ethylenedioxythiophene)-poly­(styrenesulfonate) (PEDOT–PSS) inorganic/organic composite and used in bifacial dye-sensitized solar cells (DSCs). The optical properties of SiO2/PEDOT–PSS electrode can be tailored by the blending amount of SiO2 and film thickness, and the incorporation of SiO2 in PEDOT–PSS provides better transmission in the long wavelength range. Meanwhile, the SiO2/PEDOT–PSS counter electrode shows a better electrochemical catalytic activity than PEDOT–PSS electrode for triiodide reduction, and the role of SiO2 in the catalytic process is investigated. The bifacial DSC with SiO2/PEDOT–PSS counter electrode achieves a high power conversion efficiency (PCE) of 4.61% under rear-side irradiation, which is about 83% of that obtained under front-side irradiation. Furthermore, the PCE of bifacial DSC can be significantly increased by adding a reflector to achieve bifacial irradiation, which is 39% higher than that under conventional front-side irradiation.