This journal is © The Royal Society of Chemistry. The electrodeposition of stainless steel-like FeCrNi alloys for miniaturised devices is appealing as it would allow combining excellent material properties (e.g. corrosion resistance, hardness, biocompatibility) at low-cost. However, conventional baths often contain hazardous hexavalent chromium. Cr-based alloys electrodeposited from environmentally friendly trivalent chromium electrolytes are crucial for industrial application for facilitating the transition towards sustainable and ecological production and processing. Nevertheless, this process has not been comprehensively studied or understood in depth: Especially the role of organic agents (common additives for improving Cr(iii)-based plating; e.g. glycine) in terms of material properties of the electrodeposits. The aim of this work was to investigate the electrodeposition of FeCrNi coatings from a 'green' Cr(iii)-glycine electrolyte. Novel information was attained by analysing films developed under various conditions and characterising them using a combination of advanced techniques. The evolution of microstructure (from amorphous to nanocrystalline) in correlation with film composition (i.e. metals ratio and presence of impurities) and elemental 3D spatial distribution was achieved for coatings produced from different anode materials and thermal post-treatment. The influence of Cr(iii) and glycine in terms of coating atomic contents (i.e. Fe-Cr-Ni-O-C-N-H) was evaluated for films in which both the applied current density and electrolyte composition were varied. These results, together with a thorough analysis on metals speciation/complexation allowed us to propose various Cr(iii)-based electroreduction mechanisms, and to observe, upon annealing, segregation and distribution of impurities, as well as of oxides and metals with respect to microstructure variation, providing an explanation for the amorphisation process.