Due to the inadequate photothermal conversion efficiency (PCE), most photothermal agents (PTAs) have to be used under high‐power near‐infrared (NIR) irradiation, which significantly exceeds medical safety standards, for achieving effective photothermal therapy (PTT) in antitumor treatment. This significantly hinders practical PTT application. Herein, three acceptor‐donor‐acceptor(A‐D‐A)‐type molecules are synthesized based on cyclopentadithiophene unit to develop effective PTAs. By incorporating the large‐size Si atom in the A‐D‐A molecules, the photosensitizer displays an increased packing distance in the aggregate state, leading to a blue‐shifted absorption spectrum that better matches the medial laser wavelength. Also, the Si incorporation strategy elevates the nonradiative decay rate constants (knr) of the A‐D‐A photosensitizer, and thereby a further enhancement in PCE is achieved for the PTA. Consequently, the SiO‐4F‐based nanoparticles exhibited 64.23% PCE, with excellent biosafety and photothermal stability. Under NIR irradiation with medical safety (808 nm, 0.33 W cm−2), SiO‐4F nanoparticles with 100 µg mL−1 yield a death rate of over 91% for diverse tumor cells. Moreover, in vivo experiments, SiO‐4F‐based PTT effectively inhibited and eliminated tumors. These findings suggest that the Si‐incorporated CDPT is promising for constructing effective A‐D‐A photosensitizers, enabling the PTT under NIR irradiation that meets medical safety standards.