The invention discloses a bulletproof composite armor and a preparation method thereof, and belongs to the preparation technology of ceramic and metal-based composite materials. The preparation methodof the bulletproof composite armor comprises the following steps that 1, B4C powder, carbon nanofibers, water-soluble phenolic resin and water are evenly mixed to obtain ceramic slurry, then spray drying is carried out to obtain a raw material, then cold pressing is carried out to obtain a regular hexagon green body; 2, the regular hexagon green body is put into a honeycomb of a faveolate carbonfiber mesh bag, the honeycomb is covered with carbon fiber cloth made of the same material, then vacuum hot-pressing sintering is carried out, an integral composite ceramic plate is formed; 3, the carbon nanofibers and aluminum powder are evenly mixed, an aluminum alloy bulletproof back plate is formed through powder metallurgy, forging forming and micro-arc oxidation treatment; and 4, the composite ceramic plate and the aluminum alloy bulletproof back plate are subjected to hot isostatic pressing compounding, and the bulletproof composite armor is obtained. According to the bulletproof composite armor and a preparation method thereof, the mode that a high-toughness composite ceramic is combined with the aluminum alloy back plate is adopted, so that the capacity of the composite armor forresisting multiple strikes of armor-piercing bullets and armor-piercing incendiary bullets is greatly improved.