Acrylic acid modified magnesium hydroxide nano-needles (AA–Mg(OH)2) had been synthesized by alkaline injected into magnesium chloride solution at about 0°C in the presence of acrylic acid (AA). Then the polystyrene/magnesium hydroxide nano-needles composite (PS/Mg(OH)2) had been prepared by the radical copolymerization with styrene in toluene system using AA–Mg(OH)2 as a macro-monomer. The elemental analysis (EA) and Fourier transform infrared (FTIR) analyses show that the polystyrene had been grafted onto the surfaces of the nano-needles (AA–Mg(OH)2). The nano-needles (AA–Mg(OH)2) had better dispersibility in polystyrene matrix as observed by transmission electron microscope (TEM) analysis. The thermal behavior analysis results from the differential scanning calorimetry (DSC) indicated that the magnesium hydroxide nano-needles had lower thermal decomposition temperature than that of the polymer matrix and it is expected that the nano-needles prepared by the proposed method could be used as an environmental-friendly flame retardant.