Photoelectrochemical (PEC) water splitting is an ecologically friendly technique that uses effective photoanodes to generate hydrogen (H2). The microemulsion approach was used to develop a distinctive form displaying fibrous silica-titania (FST) photoanode. We examined the photocatalytic attributes of FST, hematite (Fe2O3), and zinc oxide (ZnO). XRD, N2 adsorption-desorption, FESEM, TEM, FTIR, XPS, UV–vis/DRS, and EIS were used to investigate the FST, Fe2O3, and ZnO. By using these techniques, a bicontinuous concentric lamellar arrangement with an ample surface area has been developed within FST. Characterization results demonstrate that FST has superior catalytic activity when compared to Fe2O3 and ZnO. The FST photoanode has an improved photocurrent density of 11.75 mA/cm2 and a 14.1% Solar-to-hydrogen (STH %) efficacy, which is greater than ZnO and Fe2O3, which performed at 4.7 mA/cm2 and 2.8 mA/cm2 with 5.6% and 3.36% STH efficiency, respectively. Moreover, we also compared the Solar-to-hydrogen (STH %) effectiveness of FST with different of TiO2 photoanodes. We absorbed that the band gap is decreased when Ti is added to the silica matrix, which facilitates the formation of Si–Ti bonds. FST displays a remarkable closeness of its conduction band (CB) to the hydrogen reduction potential in comparison to ZnO and Fe2O3, allowing for quick electron transfer and rapid production of H2. The geometry of FST design provides a novel way for producing robust and exceptionally productive photoanodes for PEC water splitting.