The invention relates to a process for preparing an expandable polystyrene / silica airgel core-shell composite particle, which comprises the following steps of preparing an aqueous phase solution; preparing an oil phase solution; and after the temperature inside a reaction kettle reaches 60 DEG C, introducing the oil phase solution into the aqueous phase solution by a core-shell droplet generator, setting the temperature of the reaction kettle to be 90 DEG C, realizing the control of core-shell ratio of the composite particle by controlling the flow rate of a styrene monomer in the core-shell droplet generator, after the temperature of the reaction kettle reaches 90 DEG C, starting to time, adding pentane after 2.5 hours, after the temperature reaches 100 DEG C, keeping the temperature for 3 hours, cooling to 40 DEG C and discharging. The silica airgel / polystyrene composite heat insulation material designed by the invention simultaneously has the characteristics of low density, good mechanical properties, good flame resistance, low thermal conductivity and the like, and the heat insulation of the prepared polystyrene / silica airgel composite heat insulation board is increased by 65.4% compared with the current EPS (expandable polystyrene) board for heat insulation of buildings.