Efficient RNA extraction is critical for all downstream molecular applications and techniques. Despite the availability of several commercial kits, there is an enormous scope to develop novel materials that have high binding and elution capacities. Here we show that RNA from the cells can be extracted by dendritic fibrous nanosilica (DFNS) with higher efficiency than commercially available silica. This could be because of the unique fibrous morphology, high accessible surface area, and nano-size particles of DFNS. We studied various fundamental aspects, including the role of particle size, morphology, surface area, and charge on silica surface on RNA extraction efficiency. Infrared spectroscopy (FTIR) studies revealed the interaction of functional groups of the RNA with the silica surface, causing selective binding. Due to the sustainable synthesis protocol of DFNS, the simplicity of various buffers and washing solutions used, this RNA extraction kits can be assembled in any lab. In addition to the fundamental aspects of DFNS-RNA interactions, this study has the potential to initiate the development of indigenous DFNS based kits for RNA extraction.