As the research of photonic electronics thrives, the enhanced efficacy from an optic unit cell can considerably improve the performance of an optoelectronic device. In this regard, organic phototransistor memory with a fast programming/readout and a distinguished memory ratio produces an advantageous outlook to fulfill the demand for advanced applications. In this study, a hydrogen-bonded supramolecular electret is introduced into the phototransistor memory, which comprises porphyrin dyes, meso-tetra(4-aminophenyl)porphine, meso-tetra(p-hydroxyphenyl)porphine, and meso-tetra(4-carboxyphenyl)porphine (TCPP), and insulated polymers, poly(4-vinylpyridine) and poly(4-vinylphenol) (PVPh). To combine the optical absorption of porphyrin dyes, dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) is selected as a semiconducting channel. The porphyrin dyes serve as the ambipolar trapping moiety, while the insulated polymers form a barrier to stabilize the trapped charges by forming hydrogen-bonded supramolecules. We find that the hole-trapping capability of the device is determined by the electrostatic potential distribution in the supramolecules, whereas the electron-trapping capability and the surface proton doping originated from hydrogen bonding and interfacial interactions. Among them, PVPh:TCPP with an optimal hydrogen bonding pattern in the supramolecular electret produces the highest memory ratio of 1.12 × 108 over 104 s, which is the highest performance among the reported achievements. Our results suggest that the hydrogen-bonded supramolecular electret can enhance the memory performance by fine-tuning their bond strength and cast light on a potential pathway to future photonic electronics.