Herein, magnetic circularly polarized luminescence (CPL) (MCPL) spectroscopy was conducted to analyze an EuIII(hfa)3 complex with three chiral PIII‐ligands. Resultantly, (R)‐chirality luminophores with S‐up orientation and (S)‐chirality luminophores with N‐up orientation were observed to possess symmetrical mirror image spectra, i. e., they were enantiomers. Similarly, the (R)‐chirality luminophores with N‐up orientation and the (S)‐chirality luminophores with S‐up orientation were also enantiomers. Contrarily, (R)‐S‐up and (S)‐S‐up were diastereomers and did not possess a mirror‐image relationship. Likewise, (R)‐N‐up and (S)‐N‐up were diastereomers. The J‐dependency of gMCPL and gCPL datasets suggested that the N‐up/S‐up external magnetic field, with the aid of chiral PIII‐ligands, increased the gMCPL values by two‐ to sixteen‐fold and modulated the gMCPL signs at J=1–4. Additionally, the origins of the nonideal mirror‐symmetric CPL and MCPL spectral characteristics of EuIII(hfa)3 with three chiral PIII‐ligands were discussed in terms of parity (space‐inversion, P)‐symmetry, time‐reversal (T)‐symmetry, and PT‐symmetry laws.