In this paper we demonstrate that layer-by-layer (LbL) films of polyamidoamine (PAMAM) dendrimers and single-walled carbon nanotubes (SWCNTs) are efficient for controlling the morphology of electrogenerated cobalt (Co) and the platinum-cobalt (PtCo) alloy. While Co grew to the micrometer scale and poorly covered the ITO substrate, with the LbL matrix it was kept in the nanoscale regime and provided full substrate coverage. Pt-decorated Co nanoparticles were then generated by applying a single potential pulse in a solution containing simultaneously Co and Pt ions. Segregation of Pt and Co deposits was observed in field emission gun (FEG) images, but the PtCo alloy was probably formed to some extent according to X-ray diffraction analysis. The PtCo-LbL hybrid exhibited superior catalytic activity toward H2O2 reduction compared to the Pt-modified LbL film, which opens new prospects for applications in biosensing and fuel cells.