The acrylic adhesives with the flame-retardant property are necessary to meet the safety requirement in electrostatic flocking. In this study, acrylic emulsion chemically modified with phosphorus and silicone, PSE, with core–shell structure, was synthesized by introducing the vinyl silicone oil and phosphor-containing monomer (PAM-100) onto the molecular chain of acrylic ester polymer in the core and shell layer, respectively. Subsequently, the silicone-acrylic adhesive with flame retardation (FR-SA) was prepared by mixing PSE with inorganic flame-retardant, Al(OH)3. The acrylic adhesive obtains the excellent flame retardation under a low addition of Al(OH)3 when the ratio of PAM-100 is 5%, while the commercial adhesive needs a high addition of the inorganic flame retardant to realize the satisfactory performance. FR-SA in this work has a great potential application as intrinsically flame-retardant electrostatic flocking adhesive.