The grafting of trisilanolphenyl-polyhedral oligomeric silsesquioxanes (trisilanolphenyl-POSS) onto carbon fibers (CFs) was achieved using toluene-2,4-diisocyanate (TDI) as the bridging agent. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the successful modification of trisilanolphenyl-POSS. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images showed that trisilanolphenyl-POSS nanoparticles were grafted uniformly onto the surface of CFs and the surface roughness increased significantly. The results of dynamic contact angle (DCA) measurements demonstrated an improvement in the surface energy and wettability that related to the increased polarity of the obtained hybrid fibers (CF-g-POSS). The effects of trisilanolphenyl-POSS grafting on the interfacial, impact, and heat-resistant properties of methylphenylsilicone resin (MPSR) composites were also studied. The interlaminar shear strength (ILSS) and impact resistance of methylphenylsilicone resin (MPSR) composites after POSS modification were improved significantly with increasing amplitudes of 41.91% and 28.65%, respectively. Moreover, the interfacial reinforcing and toughening mechanisms of composites have also been discussed. In addition, the thermal oxygen aging experiments indicated a remarkable improvement in the heat oxidation resistance by the introduction of trisilanolphenyl-POSS in the interphase. Meanwhile, the grafting processes do not decrease fiber tensile strength (TS).