A low-temperature thermochemical energy storage solution can transform intermittent energy into charging capacity, yet the performance of an open thermochemical salt-hydrate reactor relies on the amount of useful storage that can be achieved per electricity unit. This paper poses a concentrated engineering inquiry: what architectural design, air flow condition, and dimension of the reactor bed will result in the highest charging quality with electricity awareness in a PV/T-assisted open thermochemical energy storage reactor? An internally consistent matrix of charging case studies will cover architecture, air flow rate, reactor bed thickness, and reactor bed length. Each case will be assessed with Electricity Aware Charging Quality Index (EACQI), which measures conversion degree, storage amount, PV/T input, external electricity consumption, power assurance rate, thermoeconomic efficiency, and electricity aware productivity. Integration of PV/T-TCES-HEX achieves a top-ranking EACQI of 1.000 while reducing external electricity demand by 59.47% compared with the TCES-alone architecture. Regarding operating cases, an air flow rate of 0.025 kg s\(^{-1}\) yields the optimal balanced charging quality while 0.020–0.030 kg s\(^{-1}\) creates the robust band for operation. The reactor bed thickness of 0.04 m provides the optimal balanced bed geometry and 0.05 m still serves as the leading alternative based on the storage priority. As for reactor bed length, 0.5 m emerges as the best choice regardless of the testing priorities. It is thus demonstrated that the best charging architecture is not achieved through maximizing conversion; rather, it is attained through integration of PV/T assistance, heat recovery, and reactor bed geometry.