The solar absorption-subcooled compression hybrid cooling system (SASCHCS) is tech-economically feasible for high-rise buildings. Since such a system operates with no auxiliary heat source, the performance coupling of its absorption subsystem and solar collectors is sensitive to the variation of hot water flow rate. In this regard, the relationship of system performance and hot water flow rate is required to be clarified exactly. Therefore, this paper aims to illustrate the effect mechanism of hot water flow rate and to propose the corresponding decision criterion. The case study is based on a typical high-rise office building in subtropical Guangzhou. The daily working process of this system with different hot water flow rates is simulated and analyzed. Subsequently, the useful heat of collectors and cooling capacity of the absorption subsystem with the hot water flow rate is discussed in detail. The results show that the SASCHCS operates with hot water temperatures ranging from 60 °C to 90 °C. The energy saving increases with the rise of hot water flow rate, but such variation tends to be flat for the excessively high flow rate. As the collector flow rate increases from 1 m3/h to 10 m3/h, the daily energy saving improves by 21% in August. Similarly, the daily energy saving increases by 37.5% as generator hot water flow rate increases from 1 m3/h to 10 m3/h. In addition, the collector flow rate of 3.6 m3/h (13.33 (kg/m2 h)) and the generator flow rate of 5.2 m3/h (19.26 (kg/m2 h)) are optimal for the annual operation, with considering power consumption of water pumps. This paper is helpful for the improvement of SASCHCS operating performance.