Here we report the fabrication of the first thin film of a zeolite-like metal–organic framework (ZMOF) with rho topology (rho-ZMOF-1, ([In₄₈(HImDC)₉₆]₄₈₋)n) in a highly oriented fashion on a gold-functionalized substrate. The oriented rho-ZMOF-1 film was functionalized by non-covalent modification via post-synthetic exchange of different probe molecules, such as acridine yellow, methylene blue, and Nile red. In addition, encapsulation of a porphyrin moiety was achieved via in situ synthesis and construction of the rho-ZMOF. Adsorption kinetics of volatile organic compounds on rho-ZMOF-1 thin films was also investigated. This study suggests that rho-ZMOF-1 thin films can be regarded as a promising platform for various applications such as sensing and catalysis.