The work aims to study the effect of pigment synergy on the decorative base paper, so as to improve the paper surface structure and optimize its physical properties. Decorative base paper was made with mixed pulp of fine hardwood and softwood (bone-dry ratio: 4∶1) which was beaten to freeness of 38°. Filler of TiO2, PAM, PAE, aluminum sulfate and other compositions was added as well. Surface coating was prepared by the adhesives of PVA and cationic starch and added with distilled water, pigment (TiO2 collaborated with Al2O3, Clay, Al2SiO5 and SiO2 respectively), dispersant, defoaming agent, lubricant and water-retaining agent. Decorative paper was coated and press polished with coating machine and calendar and then the pressing plate was dipped. Printing was conducted with the gravure to explore the effect of compound paint coating on coating structure and printability of base paper. Addition of certain SiO2 in synergistic modification was conducive to effective and uniform coating of paper surface and small pigment particles could be observed. In such case, good and tight coating structure was formed. After the decorative base paper was added with SiO2 in synergic modification, the water absorption, smoothness, dry tensile strength and wet tensile strength were improved by 135%, 130%, 175% and 160% respectively. In the aspect of printability, decorative base paper coated with SiO2 added in pigment synergistic modification showed good acceptance in relatively thinner coating, so that printing ink could be absorbed and fixed well. Moreover, dot enlargement could be controlled and the reproduction of overall tone was enlarged. Pigment synergistic modification added with SiO2 can help to improve the physical properties and printability of decorative base paper.