Traditional windows have poor thermal insulation performance, resulting in significant indoor heat loss in winter and outdoor heat entry in summer. Thermochromic smart windows can effectively block solar radiant heat by automatically adjusting light transmittance, thereby reducing air conditioning loads and leading to significant energy savings. In this study, the poly N-isopropyl acrylamide (PNIPAm)-based thermochromic hydrogel, modified MXene nanoparticles, and NiTi shape memory alloy (SMA) are integrated to endow the smart window with heat storage, temperature control, and ventilation. The smart window achieves 88.6% visible light transmission and 70% solar modulation. The inclusion of MXene nanoparticles further enhances photothermal response efficiency, while the ventilation system ensures efficient and fresh indoor air circulation. Compared to the common glass, the smart window reduces the indoor temperature by 8 °C, demonstrating its excellent temperature regulation ability. Simulation results indicate that in Shanghai, Cairo, Singapore, and Kuwait, the employment of thermochromic smart windows can reduce heating, ventilation, and air conditioning energy consumption (HVAC) by 32.6%, 49.9%, 42.7%, and 34.1%, respectively. This versatile thermochromic smart window is expected to significantly improve building efficiency and occupant comfort, offering a sustainable solution for future building designs.