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By using Bayesian spectroscopy, we studied polarization dependence of photoluminescence (PL) spectra in doubly‐split 1S yellow ortho‐excitons in a Cu2O thin‐crystal recrystallized in a small gap between paired MgO substrates. In these thin‐crystals, biaxial stresses are expected to be involved due to a small lattice mismatch between Cu2O and MgO. Under a planar‐isotropic biaxial stress, the cubic symmetry degrades to the tetragonal one in Cu2O, and subsequently, the ortho‐exciton state splits into two states having different symmetries. Consequently, the resonant PL intensities of the doubly‐split ortho‐excitons are expected to show different polarization dependencies. To elucidate such biaxial stress effect, we measured polarization dependence of the PL spectra at 4.2 K. Although resonant weak PL bands of the doubly‐split exciton states and their intense phonon sidebands co‐exist, we succeeded in decomposing to the respective spectral components by the Bayesian spectroscopy with a replica exchange Monte Carlo algorithm. As a result, it is found that the resonant PL band appearing on higher energy side shows hardly polarization dependence, whereas the resonant PL band appearing on lower energy side is further weak and shows noticeable polarization dependence. These results can be explained by the selection rule and polarization dependences on the transition matrix elements of quadrupole transitions of the doubly‐split ortho‐exciton states, and it clearly shows that the crystal symmetry degrades to D4h by the isotropic biaxial stress involved in the Cu2O thin‐crystals.