Herein, efficient chiral recognition of phosphine oxides with octahedral indium complexes was demonstrated. Direct chiral analysis of in situ-prepared phosphine oxides formed using phosphines and hydrogen peroxide was conducted effectively via P-31 nuclear magnetic resonance spectroscopy. Sufficient peak resolution of chiral phosphines was obtained consistently, thereby enabling the reliable determination of absolute chirality. Rational 1:1 binding models based on experiments and density functional theory calculations have been proposed.