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In this work, we report a family of co-halogenated two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead halogen ((PEA)2Pb(Cl/Br)4) in which the organic cation-site (PEA) is substituted with halogen at the para-site, namely the formation of 4-halophenethylamine (X-p-PEA) (X = Cl, Br; p para-site). The organic cations are regulated by introducing halogen ions at the para-site of the benzene ring to promote the structural distortion of the lead halide octahedral inorganic layer. Furthermore, (X-p-PEA) causes a shift in