The invention discloses a nano-silver/graphene composite material and a preparation method thereof. The nano-silver/graphene composite material is synthesized through the supercritical carbon dioxide (ScCO2) assisted chemical deposition method. Firstly, a silver-ammonia solution is added into reductive alcohol, and an appropriate amount of a surfactant and a complexing agent are dissolved in the reductive alcohol; afterwards, graphene oxide powder is added, and homogeneously dispersed suspension liquid is obtained after ultrasonic dispersion; then a reducing agent is added, mixed liquid is quickly transferred into a reaction kettle, CO2 gas is pumped into the reaction kettle, the reaction kettle is heated to reach set pressure and a set temperature, and at the moment, the CO2 is in a supercritical state; and after a mixed solution is stirred and reacted for a period, cooling and pressure relief are carried out, and the nano-silver/graphene composite material is obtained after repeated centrifugal cleaning and drying. The preparation method is environmentally friendly, and the prepared nano-silver/graphene composite material has the characteristics that the phase is singular, the load capacity is controllable, and nano-silver is small in grain size and evenly distributed between graphene nanosheet layers.