An extremely rare non‐Kramers holmium(III) single‐ion magnet (SIM) is reported to be stabilized in the pentagonal‐bipyramidal geometry by a phosphine oxide with a high energy barrier of 237(4) cm−1. The suppression of the quantum tunneling of magnetization (QTM) at zero field and the hyperfine structures originating from field‐induced QTMs can be observed even from the field‐dependent alternating‐current magnetic susceptibility in addition to single‐crystal hysteresis loops. These dramatic dynamics were attributed to the combination of the favorable crystal‐field environment and the hyperfine interactions arising from 165Ho (I=7/2) with a natural abundance of 100 %. An extremely rare non‐Kramers holmium(III) single‐ion magnet is reported. The suppression of the quantum tunneling of magnetization at zero field and the hyperfine structures were observed in AC magnetic susceptibility measurements, and were attributed to the combination of a favorable crystal‐field environment and the hyperfine interactions arising from 165Ho (I=7/2) with a natural abundance of 100 %.