An easy to prepare nickel-coordinated mesoporous graphitic carbon nitride (Ni-mpg-CN) was introduced as a heterogeneous photocatalyst, which efficiently accelerated the photocatalytic C–N cross-coupling of (hetero)aryl bromides and aliphatic amines, delivering the desired monoaminated products in good yields. In addition, the concise synthesis of the pharmaceutical tetracaine was accomplished in the final stage, further highlighting the practical applicability.