Adsorption is an efficient and low-cost technology used to purify volatile organic compounds (VOCs). In the current study, novel microbial adsorbents were synthesized using cells of lyophilized fungi (Ophiostoma stenoceras LLC) or bacteria (Pseudomonas veronii ZW) that were modified by aminomethylation. Based on the adsorption performance and structural characterization results, the modified fungal biosorbent was the best. Its maximum adsorption capacities for ethyl acetate, α-pinene, and n-hexane were 620, 454, and 374 mg·g, respectively, which were much higher than those of other synthesized biosorbents. The specific surface area of the fungal biosorbent was 20 m·g, and most of the components were hydrocarbon compounds and polysaccharides. The VOC adsorption process on these synthesized biosorbents was in accordance with the Langmuir isothermal model and the pseudo-first-order kinetic model, thereby suggesting that physical adsorption was the dominant mechanism. The fungal biosorbent could be used for five consecutive VOC sorption-desorption cycles without any obvious decrease in adsorption capacity.