Anhydrous organic crystalline materials incorporating imidazolium hydrogen succinate (Im-Suc), which exhibit high proton conduction even at temperatures above 100 °C, are attractive for elucidating proton conduction mechanisms toward the development of solid electrolytes for fuel cells. Herein, quantum chemical calculations were used to investigate the proton conduction mechanism in terms of hydrogen-bonding (H-bonding) changes and restricted molecular rotation in Im-Suc. The local H-bond structures for proton conduction were characterized by vibrational frequency analysis and compared with corresponding experimental data. The calculated potential energy surface involving proton transfer (PT) and imidazole (Im) rotational motion showed that PT between Im and succinic acid was a rate-limiting step for proton transport in Im-Suc and that proton conduction proceeded via the successive coupling of PT and Im rotational motion based on a Grotthuss-type mechanism. These findings provide molecular-level insights into proton conduction mechanisms for Im-based (or -incorporated) H-bonding organic proton conductors.