Recently, there has been so much interest in using biomass waste for bio-based products. Nigeria is one of the countries with an extensive availability of palm biomass. During palm oil production, an empty palm fruit bunch (biomass) is formed, and a lot of ash is generated. This study aimed to extract and characterize silica from empty palm fruit bunch (EPFB) ash using the thermochemical method. The results show that EPFB ash contains a large amount of biogenic silica in its amorphous form. It could be extracted for further use via calcination at different temperatures and compared effectively to other biomass materials, such as rice husk ash, sugarcane bagasse, and cassava periderm. The extracted silica was characterized using XRF, XRD, TGA, SEM, and FTIR, revealing the highest silica concentration of 49.94% obtained at a temperature of 800 °C. The XRF analysis showed 99.44 wt.% pure silica, while the XRD spectrum showed that the silica in EPFB is inherently amorphous. As is evident from the study, silica obtained from EPFB ash is a potential source of silica and it is comparable to the commercial silica. Thus, it is potentially usable as a support for catalysts, in the development of zeolite-based catalysts and as an adsorbent.