Indoor air quality has become a focus of people’s attention. The emission characteristics and health risks of volatile organic compounds (VOCs) and the odor emitted from polyvinyl chloride (PVC) overlaid particleboard were investigated. A synthetic index-olfactory evaluation method was used to estimate the health risks of PVC, caused by VOCs and odor based on the technology of gas chromatography-mass spectroscopy/olfactometry. Olfactory analyses and instrument detection were implemented to identify the crucial odor-active compounds. The results demonstrated that the highest concentration of VOCs and highest odor intensity occurred in the initial stage. Overall, a total of 17 odor-active compounds, including aromatic hydrocarbons, ketones, esters, alcohols, and aldehydes, were identified from PVC, while aldehydes, ketones, and esters were the most harmful constituents. Pleasant, sweet, and spicy fragrances were the key odor characteristics. It was shown that covering of the surface could effectively prevent the release of VOCs and odors, and the increased thickness would raise the emission of VOCs when the change of the total odor intensities was low. Based on the evaluation, at room temperature of 23 °C ± 1 °C, it was suggested that PVC should be stored in a well-ventilated place (more than 0.5 m3m−2h−1) for at least 28 days before it is used indoors.