This work provides a new insight into the interaction of urea with formate during the chromium electrodeposition from a sulphate-based Cr(III) solution. The influence of solution chemistry on chromium electrodeposition in a Cr(III) bath containing sodium formate and urea as complexing agents was studied by FT-IR, XPS and AFM. The results show that good quality Cr coatings may be obtained only in those cases when the secondary ligand with the carbamidic group predominates over urea in the electrolyte. This suggests that electrodeposition of good quality chromium deposit is possible due to the formation of active chromium-carbamid complexes [Cr(carbamid)(n)(H2O)(6-n)](3+). These complexes delay the formation of the stable oligomeric species, and thus provide a prolonged working lifetime in the Cr(III) formate-urea electrolyte.