The unusual T-shaped XH…π hydrogen bonds between HF and BB or CC multiple bonds are compared using the (U)MP2 and DFT ((U)B3LYP functional) methods with the 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. The binding energies follow the order of HBBH ( 1 Δ g )…HF>H 2 CCH 2 …HF>HCCH…HF>OCBBCO…HF>HBBH (3Σg-)…HF. NBO analysis and the results of the AIM charge density and electron density shifts confirm that, although BB multiple bonds are more electron-deficient than CC multiple bonds, HBBH ( 1 Δ g ) can be as the stronger T-shaped XH…π hydrogen-bond proton acceptor than the CC multiple-bond monomers.