Vibrational energy relaxation dynamics of the excited hydrogen-bonded (H-bonded) OH conjugated with free OH (OD) at an air/water (for both pure water and isotopically diluted water) interface are elucidated via non-equilibrium ab initio molecular dynamics (NE-AIMD) simulations. The calculated results are compared with those of the excited H-bonded OH in bulk liquid water reported previously. In the case of pure water, the relaxation timescale (vibrational lifetime) of the excited H-bonded OH at the interface is T1 = 0.13 ps, which is slightly larger than that in the bulk (T1 = 0.11 ps). Conversely, in the case of isotopically diluted water, the relaxation timescale of T1 = 0.74 ps in the bulk decreases to T1 = 0.26 ps at the interface, suggesting that the relaxation dynamics of the H-bonded OH are strongly dependent on the surrounding H-bond environments particularly for the isotopically diluted conditions. The relaxation paths and their rates are estimated by introducing certain constraints on the vibrational modes except for the target path in the NE-AIMD simulation to decompose the total energy relaxation rate into contributions to possible relaxation pathways. It is found that the main relaxation pathway in the case of pure water is due to intermolecular OH⋯OH vibrational coupling, which is similar to the relaxation in the bulk. In the case of isotopically diluted water, the main pathway is due to intramolecular stretch and bend couplings, which show more efficient relaxation than in the bulk because of strong H-bonding interactions specific to the air/water interface.