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Organic or inorganic (A) metal (M) halide (X) perovskites (AMX(3)) are semiconductor materials setting the basis for the development of highly efficient, low-cost and multijunction solar energy conversion devices. The best efficiencies nowadays are obtained with mixed compositions containing methylammonium, formamidinium, Cs and Rb as well as iodine, bromine and chlorine as anions. The understanding of fundamental properties such as crystal structure and its effect on the band gap, as well as their phase stability is essential. In this systematic study X-ray diffraction and photoluminescense spectroscopy were applied to evaluate structural and optoelectronic properties of hybrid perovskites with mixed compositions.