Desiccant air-conditioning systems are considered a competitive alternative to conventional vapor compression cycles. However, the literature lacks detailed studies of such systems when coupled with thermally active buildings and powered by solar energy due to the complexity of modeling and controlling the system. In the present study, a novel hybrid desiccant-dehumidification-absorption system, driven by external compound parabolic concentrators (DDA-XCPC), is used to serve a typical office space in a hot climate zone. The entire system is modeled and simulated dynamically in the TRNSYS environment. The current study investigates the proposed system performance in terms of the achieved thermal comfort, energy consumption, solar fraction, life cycle costs, and carbon emissions. The results reveal superior thermal comfort levels with percentages of people dissatisfied below 5.6 %. The daily solar fraction ranged between 41 and 90 %, with an average of 49 %, whereas the coefficient of performance varied between 0.46 and 1.38 while having a season average of 0.86. Compared to a conventional system, driven by a gas boiler, the proposed system increased the life cycle costs by 6,824 USD due to the large capital investment of the solar thermal loop. However, each 1,000 USD of additional expenses was accompanied by a cutdown of 4,619 kg of CO2 emissions. Increments in the solar system’s capacity (i.e., solar collector area and storage tank volume) have adverse and favorable impacts on the economic and environmental performances, respectively. Therefore, the system can be a viable option whenever green energy production is prioritized and considerably incentivized.