A high-frequency, piezoelectric thin-film sensor was successfully deposited on a nickel-based superalloy bolt by radio frequency magnetron sputtering to develop a smart, nickel-based superalloy bolt. Ultrasonic response characterization, high accuracy, and repeatability of ultrasonic measurement of axial preload in nickel-based superalloy smart bolts are reported here and were fully demonstrated. The axial preload in the nickel-based superalloy smart bolt was directly measured by the bi-wave method (TOF ratio between transverse and longitudinal-mode waves) without using the traditional integration of a longitudinal and shear transducer. A model concerning the bolt before and after tensioning was established to demonstrate the propagation and displacement distribution of the ultrasonic waves inside a nickel-based superalloy smart bolt. The measured A-scan signal presented significantly favorable features including a mixture of transverse and longitudinal mode waves, a pure and broad frequency spectrum which peaked at 17.14 MHz, and high measurement accuracy below 3% for tension of 4 kN–20 kN. For the temporal ultrasonic signal, the measurement envelopes were narrower than for the counterpart of the simulation, justifying the ‘filtration’ advantage of the high-frequency sensor. Both the TOF change of the single longitudinal-mode wave and the TOF ratio between transverse- and longitudinal-mode waves increased linearly with preload force in the range of 0 kN to 20 kN. Compared with the commercial piezoelectric probe, the proposed probe, based on the combination of a high-frequency, piezoelectric thin-film sensor and a magnetically mounted transducer connector, exhibited high tolerance to temperatures as high as 320 °C and high repeatability free from some interference factors such as bolt detection position change and couplant layer thickness. The results indicate that this system is a promising axial preload measurement system for high-temperature fasteners and connectors, and the proposed sensor is a practical, high-frequency ultrasonic sensor for non-destructive testing.