A novel Zn–Al layered double hydroxide nanosheet (ZnAl NS) based nanosphere film has been fabricated on an indium tin oxide (ITO)-coated glass plate substrate from a transparent colloidal suspension of ZnAl NS via an electrophoretic deposition (EPD) method. The morphology of the as-deposited film can be tailored by adjusting the deposition time and further heat treatment above 450 °C affords a Zn–Al mixed metal oxide (MMO) nanosphere film. We propose that the novel nanosphere microstructure of the ZnAl NS film results from the formation of diamond like carbon (DLC) precursor material, by electrolytic decomposition of formamide during the EPD process, which precipitates the ZnAl NS to lead to nuclei which develop into nanospheres.