The precise measurement of neutron star (NS) spins can provide important insight into the formation and evolution of compact binaries containing NSs. While traditional methods of NS spin measurement rely on pulsar observations, gravitational-wave detections offer a complementary avenue. However, determining component spins with gravitational waves is hindered by the small dimensionless spins of the NSs and the degeneracy in the mass and spin parameters. This degeneracy can be addressed by the inclusion of higher-order modes in the waveform, which are important for systems with unequal masses. This study shows the suitability of NS–black hole mergers, which are naturally mass-asymmetric, for precise NS spin measurements. We explore the effects of the black hole masses and spins, higher-mode content, inclination angles, and detector sensitivity on the measurement of NS spin. We find that networks with next-generation observatories like the Cosmic Explorer and the Einstein Telescope can distinguish NS dimensionless spin of 0.04 (0.1) from zero at 1σ confidence for events within ∼350 (∼1000) Mpc. Networks with A+ and A♯ detectors achieve similar distinction within ∼30 (∼70) Mpc and ∼50 (∼110) Mpc, respectively.