To better utilize clean energy for the purpose of carbon neutrality, we designed and prepared the three-phase connected ternary tandem heterojunctions for the photocatalytic hydrogen evolution reaction. Notably, the variety bonding rings demonstrated by density functional theory raised the possibility of a special electrons transferred mechanism. Further, a unique ring electrons transfer mechanism extended the lifetime of the excitons and promoted their separation and transfer. In-situ XPS (X-ray photoelectron spectroscopy) and other characterizations were used to thoroughly characterize the ring electron transfer. The addition of the mid-component in three phase-connected heterojunctions changed the pathway of electrons transfer and increased photocatalytic hydrogen evolution reaction efficiency. As a consequence, this heterojunction exhibited an enhanced exciton lifetime, low exciton–hole recombination rate, and good photoelectric response, thus outperforming a traditional tandem heterojunction by 14.6%. This work provides novel insights into the directionally design, construction, and optimization of photocatalyst structures and exciton transfer mechanisms.