Post-synthetic dealumination treatment is a common tactic adopted to improve the catalytic performance of industrialized zeolitic catalysts through enhancements in acidity and stability. However, among the possible extra-framework aluminum (EFAL) species in dealuminated zeolites such as Al3+, Al(OH)(2+), Al(OH)(2)(+), AlO+, AlOOH, and Al(OH)(3), the presence of tri-coordinated EFAL-Al3+ species, which exhibit large quadrupolar effect due to the lack of hydrogen-bonding species, was normally undetectable by conventional one- and two-dimensional H-1 and/or Al-27 solid-state nuclear magnetic resonance (SSNMR) techniques. By combining density functional theory (DFT) calculations with experimental P-31 SSNMR using trimethylphosphine (TMP) as the probe molecule, we report herein a comprehensive study to certify the origin, fine structure, and possible location of tri-coordinated EFAL-Al3+ species in dealuminated HY zeolite. The spatial proximities and synergies between the Bronsted and various Lewis acid sites were clearly identified, and the origin for the observed EFAL-Al3+ species with ultra-strong Lewis acidity was deduced to be at the expense of adjacent Bronsted acid sites. The excellent performance of such tri-coordinated EFAL species was furthermore confirmed by glucose isomerization reactions.