Zn–Mn electrodeposition onto Pt from an electrolyte containing boric–sorbitol complex (BSC) or boric acid alone (BA) was studied. The influence of BA or BSC content on the deposition process was investigated by cyclic voltammetry and electrodeposits, produced potentiostatically, were analysed by SEM, EDX, and XRD. The voltammetric studies indicated that an increase in the BSC concentration led to a decrease in the deposition current density. EDX analysis of deposits obtained at −1.60 V showed that increasing the BA or BSC concentration in the bath induced a fall in the Mn content of the electrodeposit and that for BSC this decrease was more significant. SEM images showed that the Zn–Mn electrodeposit obtained in the presence of 0.24 M BSC were smoother than other deposits; hence, BSC acted as a grain refiner at this concentration. XRD analysis of this deposit indicated that it was composed of Zn, Mn, MnZn13, and MnH0.8.