Conductive additive-impregnated polylactic acid can be coated with vanadium oxide (V2O5) by electrodeposition. By thermal pre-treatment of the thermoset printed electrode structure comprising a graphite-PLA composite, the conductivity of the composite material is improved by exposing the graphite at the outer surface by surface segregation, that is ordinarily buried within the plastic. This promotes quite effective electrodeposition under potentiostatic conditions, allowing conformal coating a complex electrode surface and structure with V2O5. The surface coating and electrode were analysed using Raman scattering spectroscopy, X-ray diffraction, energy dispersive X-ray analysis and scanning electron microscopy, and details the relationship between electrodeposition parameters and the quality of the deposit on the PLA electrode.