In the chemical industry, the separation of the acetic acid from the HAc/H2O system is always influenced by the hydrogen bonding. In the present work, an investigation on the hydrogen bonding of various hydrates of double acetic acid (HAc) molecules is carried out with two first-principle methods including ab initio molecular dynamics (AIMD) simulation and quantum chemical calculations (QCC). From the AIMD simulation, the distribution of the head-on rings of acetic acid is revealed and shows that the favorable structures tend to be the acetic acid hydrates rather than the HAc cyclic dimer. The 6- and 10-membered head-on rings involving single and double HAc molecules, respectively, appear to be the dominant structures. According to the QCC, the most stable structure is found to be the conformer with the biggest head-on ring in each group. The energetics of the rings indicates that the stability of the ring increases with increased ring size (with the exception of the 9-membered ring), and the 10-membered ring is the most stable. The relative stability of the ring structures implied by the static QCC result is in good agreement with the statistical ring distribution of the AIMD simulation.