In nonlinear ultrasonic testing, the quadratic and more recently cubic nonlinearity parameters are frequently measured as a quantitative indicator of damaged material state. Application of higher-order harmonics can improve the sensitivity of detection and monitoring for damages and microstructures due to their higher values of nonlinearity parameters. The excitation and reception of higher-order harmonics, so-called superharmonics, which use the third to fifth harmonics arising from nonlinear wave propagation, is not sufficiently investigated and applied. The purpose of this communication is to develop a highly sensitive superharmonic nondestructive technique that efficiently generates and receives third- and fifth-order harmonics using the odd harmonic resonances of a single piezoelectric crystal. The method focuses on the measurement of fifth harmonic generation and reception, and the calculation of the relative quintic nonlinearity parameter (δ’). The method also addresses the issue of source nonlinearity that may be contained in the measured fifth harmonic amplitude. The measurement results ofδ’for a series of precipitation heat-treated samples clearly show a much better sensitivity than the results of the cubic nonlinearity parameter (γ’). The proposed method enables a highly sensitive and true pulse-echo mode nonlinear ultrasound testing.