Multifunctional nanofibers for particulate matter (PM) and volatile organic compounds (VOCs) removal from the indoor atmospheric environment were manufactured from eco-friendly natural cellulose materials via electrospinning using an optimized solvent system containing 1-ethyl-3-methylimidazolium acetate (EmimAC) and dimethylformide (DMF) in a 3:7 volume ratio. EmimAC improved the cellulose stability, whereas DMF improved the electrospinnability of the material. Various cellulose nanofibers were manufactured using this mixed solvent system and characterized according to the cellulose type, such as hardwood pulp, softwood pulp, and cellulose powder, and cellulose content ranging from 6.0–6.5 wt%. The correlation between the precursor solution alignment and electrospinning properties indicated an optimal cellulose content of 6.3 wt% for all cellulose types. The hardwood pulp-based nanofibers possessed the highest specific surface area and exhibited high efficiency for eliminating both PM and VOCs, with a PM2.5adsorption efficiency of 97.38%, PM2.5quality factor of 0.28, and toluene adsorption of 18.4 mg/g. This study will contribute to the development of next-generation eco-friendly multifunctional air filters for indoor clean-air environments.