We report on a nonoxidative topochemical route for the synthesis of a novel indate-based oxyfluoride, LaBaInO3F2, using a low-temperature reaction of Ruddlesden-Popper-type LaBaInO4 with polyvinylidene difluoride as a fluorinating agent. The reaction involves the replacement of oxide ions with fluoride ions as well as the insertion of fluoride ions into the interstitial sites. From the characterization via powder X-ray diffraction (PXRD) and Rietveld analysis as well as automated electron diffraction tomography (ADT), it is deduced that the fluorination results in a symmetry lowering from I4/mmm (139) to monoclinic C2/c (15) with an expansion perpendicular to the perovskite layers and a strong tilting of the octahedra in the ab plane. Disorder of the anions on the apical and interstitial sites seems to be favored. The most stable configuration for the anion ordering is estimated based on an evaluation of bond distances from the ADT measurements via bond valence sums (BVSs). The observed disordering of the anions in the oxyfluoride results in changes in the optical properties and thus shows that the topochemical anion modification can present a viable route to alter the optical properties. Partial densities of states (PDOSs) obtained from ab initio density functional theory (DFT) calculations reveal a bandgap modification upon fluoride-ion introduction which originates from the presence of the oxide anions on the interstitial sites. The photocatalytic performance of the oxide and oxyfluoride shows that both materials are photocatalytically active for hydrogen (H2) evolution.