Conventional cellulose diacetate filter tips of cigarette (CDFTC) are poor filtration performance of toxic compounds. However, environmentally benign filter tips can be made by replacing cellulose diacetate fibers with various types of natural fibers. In the present work, the blocking and filtering effect of natural fibers such as cotton and wool was examined with regards to the polycyclic aromatic hydrocarbons (PAHs) present cigarette smoke. Using various techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and Fluorescence detection, the blocking and filtering mechanisms were investigated in detail. The results showed that compared with CDFTC, the filter tips made from natural fibers (cotton or wool) were investigated superior at filtering out toxic particles, which is mainly due to the natural twist or crimp along with their longitudinal directions. The efficiency of PHAs removal by the cotton and wool fibers reached 71.0% (with absorption of up to 71.0 µg cig −1 ) and 60.5% (with absorption of up to 60.5 µg cig −1 ), respectively. Compared with the Zhongnanhai filter tip used in this study (54.0%), the filtration efficiency of the cotton and wool fibers was increased by 17.0% and 6.5%, respectively.