The invention discloses a sym-trinitrobenzene and azole explosive co-crystallized explosive preparation method, which comprises: 1, preparing a TNB and azole co-crystallized solution; and 2, preparing a TNB/azole co-crystallized explosive: placing the TNB and azole explosive co-crystallized solution in a spraying tank, regulating spraying pressure to 0.2-0.6 Mpa, opening a valve, spraying the co-crystallized solution into a collection tank under the effect of high pressure gas flow, contacting stirred non-solvent water, rapidly precipitating a crystal, filtering, and drying to obtain the TNB/azole co-crystallized explosive. The invention further discloses a TNB and MDNT co-crystallized explosive. According to the present invention, the prepared TNB and MDNT co-crystallized explosive has low melting point and high energy density, can be used as the novel casting liquid phase carrier, and has good application prospect in the field of ammunition casting; and the preparation method has advantages of simple process and convenient operation.