Compositional and structural elucidation of the materials is important to know their properties, chemical stability, and electro-photoactivity. The heterojunction electrocatalyst and photocatalyst activity could open a new window for solving the most urgent environmental and energy problems. Here, for the first time, we have designed and fabricated Bi 2 O 3 /bismuth titanates modified with MOF-In 2 S 3 /CdIn 2 S 4 materials by a stepwise process. The detailed structural elucidation and formation of mixed composite phases were studied in detail. It has been found that the formed composite was efficiently utilized for the electrocatalytic H 2 production reaction and the photocatalytic degradation of tetracycline. XRD patterns for the metal−organic framework-In 2 S 3 showed a main compound of MOF, and it was assigned to a MIL-53 MOF phase, with a monoclinic structure. The addition of CdCl 2 onto the MOF-In 2 S 3 phase effectively produced a CdIn 2 S 4 flower platform on the MOF rods. The uniform dispersion of the bismuth titanates in MOF-In 2 S 3 /CdIn 2 S 4 materials is detected by mapping of elements obtained by dark-field HAADF-STEM. Finally, the predictions of how to integrate experiments and obtain structural results more effectively and their common development in new heterojunctions for electro-/photocatalytic applications are presented.