Wood staining is a crucial technique for enhancing the decorative effect of wood. Different mordants and mordant processes can influence the staining effect of wood. In this study, three types of mordants and mordant methods were selected to improve the color difference and colorfastness to the washing of poplar veneer, using green peanut pigment as the dye. An orthogonal test was conducted to investigate the effects of mordant temperature, mordant time, and mordant concentration on color difference and colorfastness to washing. Range and variance analysis were employed to determine these properties’ main factors. A fuzzy comprehensive evaluation method was used to evaluate and optimize the color difference value and colorfastness of washing. The results revealed that all three factors had significant impacts on both color difference and colorfastness to washing during the process of mordant staining. The optimal process conditions (temperature, concentration, time) for achieving desirable staining effects on poplar veneer were determined as 50 °C, 0.8%, and 2 h, respectively. Furthermore, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) analyses demonstrated that the dye formed complexes with poplar wood, enabling it to adhere to wood grain apertures and tube walls effectively. Mordant treatment increased the crystallinity of stained wood significantly while improving its overall staining performance considerably. This study provides substantial data support for future optimization processes involving natural pigment coal staining in wood.