As a green filler comprising both nano- and micro-sized fibrils, micro/nano white bamboo fibrils (MWBFs) were treated with a silane coupling agent (S-MWBFs) prior to their introduction in an epoxy resin (EP). The sequential processes of steam explosion, alkaline treatment, and micro grinding were used to prepare to MWBFs. The effects of the S-MWBFs on various characteristics of the cured EP such as compatibility, fracture toughness, morphology, mechanical property, and flame retardation were studied. The fracture toughness and mechanical characteristics of both the storage modulus and tanδ maximum increased following addition of the S-MWBFs to the EP. Notably, the fracture toughness of the EP with 0.3 wt% of S-MWBFs was 22.2% higher than that of unmodified resin. Scanning electron microscopy presented somewhat rougher surfaces with shear deformation and tortuously twisting cracks, resulting in a higher fracture toughness in S-MWBF-modified epoxy samples. However, fire testing showed that the presence of S-MWBFs increased the burning rate of the EP.