Herein, we report a type of enhanced ammonia (NH₃) sensing materials formed by the functionalization of reduced graphene oxide (RGO) with 1,8,15,22-tetra-(4-tert-butylphenoxyl)-metallophthalocyanine (TBPOMPc, M = Cu, Ni, and Pb) via a solution self-assembly method based on π–π stacking interactions. The RGO/TBPOMPc hybrids exhibit excellent sensitivity, high response value, and fast response and recovery at room temperature, especially the RGO/TBPOPbPc sensor. The enhancement of the NH₃-sensing performance by TBPOMPc with a rigid phenoxyl-substituted group is attributed to the self-assembly behavior of TBPOMPc molecules. The rigid structure of TBPOMPc effectively prevents the intermolecular aggregation behavior. On the one hand, it expands the specific surface area of the RGO/TBPOMPc hybrids, which is propitious for the physical adsorption and diffusion of NH₃ molecules and reduces the response and recovery time. On the other hand, it weakens the electronic interaction between TBPOMPc molecules and results in reducing the resistance of charge transfer from NH₃ to TBPOMPc. Moreover, TBPOMPc is beneficial to enhance the sensitivity and selectivity of the RGO/TBPOMPc sensors towards NH₃. By contrast, the response of various RGO/TBPOMPc sensors decreases in the order of RGO/TBPOPbPc > RGO/TBPOCuPc > RGO/TBPONiPc. Furthermore, the rigid structure and central metals of TBPOMPc play a critical role in the sensitivity of NH₃, as evidenced from the scanning tunneling microscopy, current–voltage characteristics, and electrochemical impedance spectra.