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Massive He stars are potential candidates of type Ib/c supernova (SN) progenitors. Understanding their final fates remains a key issue in astrophysics. In this work, we investigate the evolution of He stars with initial masses from 5 M ⊙ to 65 M ⊙ , focusing on the presupernova (pre-SN) core structures to assess their explodability. Our simulations indicate that the final core structure is determined by the CO core mass and the central 12 C mass fraction at the end of core He burning, affecting the properties of central C-burning and the locations of convective shells. The location of the last convective C-burning shell sets the mass of the C-free core, constraining the iron core mass and compactness. We found that the final compactness and iron core mass exhibit non-monotonic behavior with initial mass, suggesting that the boundary between neutron star and black hole formation is not a simple mass threshold. This is due to core C/Ne burning becoming neutrino dominated. This process drives stronger core contraction, ultimately increasing the iron core mass and the final compactness. In contrast, earlier core Ne/O/Si ignition and shell mergers inhibit core contraction, reducing both the iron core mass and final compactness. We also discuss the effects of metallicity and overshooting on the pre-SN core structure. These factors potentially affect the explodability of progenitors.