Because the surface of MDF is not aesthetically pleasing, it usually needs to be veneered and then painted, but such a board releases harmful VOCs, among which Benzene Series is the most harmful. Benzene and its series are a group of carcinogenic compounds. With the diluents of nitrocellulose (NC)-lacquered MDF as the research objects, the release of the Benzene Series was studied to provide a scientific basis for pollution control and a reference for eco-friendly paint production. The attenuant of NC paint, anhydrous ethanol, ethyl acetate and solvents mixed with different alcohol ester ratios were used as diluents in NC lacquer. Two kinds of wood-veneered MDF with different thickness (18 mm and 8 mm) were coated with NC lacquer and analyzed in the experiment. The gas was collected using a small environmental chamber and the Benzene Series was analyzed using GC-MS. The concentration of Benzene Series released by MDF was 316.24 μg·m−3, and that of the NC-lacquered MDF with thicknesses of 18 mm and 8 mm were 284.44 μg·m−3 and 281.06 μg·m−3, respectively. The MDF released 14 kinds of Benzene Series, and the NC-lacquered MDF with two thicknesses released 18 kinds of it. The release concentration order of Benzene Series in NC-lacquered MDF with different diluents of the 18 mm thick panel was NC-M, NC-A, and NC-E from high to low. The lowest concentration of it occurred when the ratio of anhydrous ethanol to ethyl acetate was 1:3, and the lowest amount of components were at the ratio of 1:2. The concentration of Benzene Series released by MDF is higher than that released by the NC-lacquered MDF. Thickness has no effect on the type of release. The thicker MDF was, the higher the concentration was. The alcohol and ester thinner can control the release of Benzene Series from the source, and the optimal mixing ratio was 1:3.