Owing to the flexibility and high-frequency responsiveness, nanocomposite piezoresistive sensors are suitable for Lamb wave detection on composite materials. Various types of nanocomposite films have been developed for this purpose. However, the inelasticity trait of commonly used electrodes for the nanocomposite films impedes their application on the nonplanar surface of composites. Herein, an in situ prepared piezoresistive film based on graphene and polymethyl methacrylate nanocomposite has been proposed for ultrasonic wave detection on nonplanar carbon fiber-reinforced composites. Electrospinning method is employed to fabricate piezoresistive fiber film onto carbon fiber-reinforced polymer (CFRP) composites, and the sensitivity along the thickness direction is utilized via employing the CFRP layer as one electrode. The fabricated sensitive films exhibit the capability to detect up to 150 kHz ultrasonic signals on curved surfaces. With the help of Hilbert energy spectrum, the precise damage localization on CFRP is achieved by the sensitive film array with a relative error of only 1%. This innovation provides a new in situ preparation method for ultrasonic sensitive film on nonplanar-shaped CFRP components for nondestructive evaluation task.