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Very volatile organic compounds (VVOCs) are a group of important odor pollutants affecting indoor air quality that have been shown to be harmful to human health. A 15 L environmental chamber, combined with multi-bed tube was used to collect gases. Fifteen very volatile organic compounds (VVOCs), including 12 odor compounds, were identified from veneered medium density fiberboard coated with water-based lacquer (WB-MDF) using gas chromatography–mass spectrometry/olfactometry (GC-MS/O). The total very volatile organic compound (TVVOC) and total odor intensity (TOI) showed a decreasing trend over time, reaching equilibrium on day 28. TVVOC showed an overall slow-fast-slow emission profile, from day 3 to day 7, with a maximum decay rate of 29.7%. TOI showed the greatest rate of decline from day 1 to day 3, at approximately 12%. Alkane and alcohol VVOCs were the more abundant compounds, accounting for at least 60% and even up to 80% of the total. The major odor impression was fruity, with a highest odor rating of 6.6, followed by sweet, with an odor rating of 6.1. Although the odor impression changed from sweet to fruity over time, it seemed pleasant overall. The odor contributors were mainly alkanes, alcohols, esters, and ethers, which had relatively high odor intensities. The main odor-contributing substances were dichloromethane, ethanol, ethyl acetate, 2-methylacrylic acid methyl ester, and tetrahydrofuran. When WB-MDF is used for furniture or other decorative materials, it is strongly recommended that it be stored under ventilation for at least 28 days and the adoption of substitute solvents of lacquers, modified adhesives, and low-odor wood raw materials is recommended. These possible initiatives would contribute to the aim of building an environmentally friendly indoor environment.