In this work, PLLA and CD/PLLA nanofibers were fabricated using electrospinning and utilized as a particulate matter (PM) and volatile organic compounds (VOCs) filter. The electrospun PLLA and CD/PLLA were characterized with various techniques, including SEM, BET, FTIR, XRD, XPS, WCA, DSC, tensile strength testing, PM and VOCs removal efficiency, and triboelectric performance. The results demonstrated that the best air filter was 2.5 wt%CD/PLLA, which performed the highest filtration efficiencies of 96.84 ± 1.51% and 99.38 ± 0.43% for capturing PM and PM, respectively. Its PM removal efficiency was 16% higher than that of pure PLLA, which were contributed by their higher surface area and porosity. These 2.5 wt%CD/PLLA nanofibers also exhibited the highest and the fastest VOC entrapment. For triboelectric outputs, the 2.5 wt%CD/PLLA-based triboelectric nanogenerator provided the highest electrical outputs as 245 V and 84.70 μA. These give rise to a three-fold enhancement of electrical outputs. These results indicated that the 2.5 wt%CD/PLLA can improve surface charge density that could capture more PM via electrostatic interaction under surrounding vibration. Therefore, this study suggested that 2.5 wt%CD/PLLA is a good candidate for a multifunction nanofibrous air filter that offers efficient PM and VOC removal.