Boron phenolic resin is widely used in the aerospace field because of its excellent thermal properties. In this article, nitrile rubber powder was added to phenolic resin to modify fiber-reinforced phenolic resin composites. The results showed that the tensile strength continued to decrease; the elongation ratio increased from 20.01% to 32.04%; and flexural strength and flexural modulus reached the highest values of 188 and 9,401 MPa, respectively. Thermal analysis showed that rubber had little effect on the heat resistance at low temperatures, especially below 350°C. Furthermore, the coefficient of thermal expansion of the composites increased from 8.9 × 10−6 to 1.5 × 10−5 K−1, increasing by nearly 70%. The electron microscopy images showed a tortuous fracture path in modified composites, which indicated that rubber powder–modified phenolic composites had a ductile fracture.