High entropy material demonstrates several effects from multi-component composition, which is potential in the catalytical field. During this decade, combining the mechanical force-driven piezoelectric/ferroelectric catalysts with photocatalysts has attracted much attention due to the separation of photogenerated carriers, leading to synergistic catalytic activities. This study reports a novel composite of high entropy oxide (CaZrYCeCr)O₂ with unique ferroelectric properties mixing with bismuth titanate (Bi₄Ti₃O₁₂) microplates, improving the piezo-phototronic catalytic activities. The results show that high entropy oxide catalyst (CaZrYCeCr)O₂ mainly consists of the porous structure with multivalent transition metal substitution, contributing to severe lattice distortion. Consequently, the precipitation of disordered phase Ca(Zr_1-xCr_x)O₃(x=0.05~0.1) caused by lattice distortion was decorated on the porous framework. In addition, Ca(Zr_1-xCr_x)O₃ with a non-centrosymmetric structure exhibits ferroelectric property and plays a vital role in separating the electron-hole pairs, which performs higher degradation efficiency around 588 % compared to pristine ZrYCeO_2. Additionally, the ferroelectric Bi₄Ti₃O₁₂ was considered to construct a Z-scheme catalytic activity and form a heterojunction high entropy oxide. Furthermore, we demonstrated that morphotropic phase boundaries between Bi₄Ti₃O₁₂ and CaZr_1-xCr_xO₃ could dramatically enhance the ferroelectric property and promote the performance of the piezo-phototronic activities, revealing that CaZrYCeCrO₂/ Bi₄Ti₃O₁₂ could be an innovative catalyst in the future.