One of the most important challenges of modern science and technology is the quest for novel and tuneable materials, the properties of which can be widely controlled by chemical modifications or external stimuli. Simultaneously, an interest in the development of magnetic thin films also gains significant attention. In the current paper we bring together both these challenges and present a study of a new type of low-dimensional nickel hexacyanoferrate/chromate system. Thin films were obtained by the “layer by layer” deposition technique, where the ratio of Fe/Cr was controlled by the dipping sequence. The scope of this work is a comprehensive analysis of structural, spectroscopic and magnetic properties of the compound and the investigation of the evolution of material properties induced by the change of the chemical composition.