Seasonal variation and spatial distribution of PM2.5 bound polycyclic aromatic hydrocarbons (PAHs) were investigated at urban residential, commercial area, university, suburban region, and industry in Xi'an, during summer and winter time at 2013. Much higher levels of total PAHs were obtained in winter. Spatial distributions by kriging interpolations principle showed that relative high PAHs were detected in western Xi'an in both summer and winter, with decreasing trends in winter from the old city wall to the 2nd-3rd ring road except for the suburban region and industry. Coefficients of diversity and statistics by SPSS method demonstrated that PAHs in suburban have significant differences (t < 0.05) with those in urban residential in both seasons. The positive Matrix Factorization (PMF) modeling indicated that biomass burning (31.1%) and vehicle emissions (35.9%) were main sources for PAHs in winter and summer in urban, which different with the suburban. The coal combustion was the main source for PAHs in suburban region, which accounted for 46.6% in winter and sharp decreased to 19.2% in summer. Scattered emissions from uncontrolled coal combustion represent an important source of PAHs in suburban in winter and there were about 135 persons in Xi'an will suffer from lung cancer for lifetime exposure at winter levels. Further studies are needed to specify the effluence of the scattered emission in suburban to the city and to develop a strategy for controlling those emissions and lighten possible health effects.