The structural properties and whiteness of the substrate surface markedly effect printing quality and are closely related to the primer coating processes. Herein, four different roller coating schemes were applied on MDF surfaces to change their structural properties and color, and the whiteness, gloss, and roughness properties of the substrate surfaces were characterized for UV inkjet printing. Data analysis was conducted to explore the effects of these variables on the color reproduction, relative contrast, and printing gloss of the MDF substrates. The results showed that, according to CMYK, L*a*b* values and spectral reflectance data, the finishing of the MDF substrate with a 40 g/m2 layer of transparent primer combined with three layers of white primer at 20 g/m2 per roll coating layer had the best color reproduction effect for UV inkjet printing. Regarding the effects of relative contrast, the correlation with whiteness and glossiness was significant, while the correlation with glossiness was minor. The inkjet printing gloss value was positively correlated with substrate primer surface whiteness, while it was negatively correlated with roughness. When the surface whiteness of the substrate was relatively high, the roughness was lower and the printing effects were glossier. We sought to optimize the printing effects of all aspects of the MDF substrate by primer coating. The results of this work provide a feasible application method to improve printing quality and enhance the added value of low-quality boards, as well as to further expand the application of UV inkjet printing in the wood decoration market.