One of the greatest challenges in the enhancement of the electrical properties of conductive mayenite [Ca24Al28O64]4+(4e-) (hereinafter C12A7:e-) is the design of a more suitable/simple synthesis strategy that can be employed to obtain the required properties such as excellent stable electrical conductivity, a high electron concentration, outstanding mobility, and an exceptionally large surface area. Therefore, to synthesize C12A7:e- in the metallic state, we proposed a facile, direct synthesis strategy based on an optimized sol-gel combustion method under a nitrogen gas environment using the low-cost precursors Ca(NO3)2·4H2O and Al(NO3)3·9H2O. Using this developed strategy, we successfully synthesized moderately conductive nanoscale C12A7:e- powder, but with unexpected carbon components (reduced graphene oxide (rGO) and/or graphene oxide (GO)). The synthesized C12A7:e- composite at room temperature has an electrical conductivity of about 21 S cm-1, a high electron concentration of approximately 1.5 × 1021 cm-3, and a maximum specific surface area of 265 m2 g-1. Probably, the synthesized rGO was coated on nanocage C12A7:e- particles. In general, the C12A7:e- electride is sensitive to the environment (especially to oxygen and moisture) and protected by an rGO coating on C12A7:e- particles, which also enhances the mobility and keeps the conductivity of C12A7:e- electride stable over a long period. Doped mayenite electride exhibits a conductivity that is strongly dependent on the substitution level. The conductivity of gallium-doped mayenite electride increases with the doping level and has a maximum value of 270 S cm-1, which for the first time has been reported for the stable C12A7:e- electride. In the case of Si-substituted calcium aluminate, the conductivity has a maximum value of 222 S cm-1 at room temperature.