This work presents the enhanced corrosion resistance of newly developed two-layer composite coatings deposited on low-carbon steel: electrodeposited zinc alloy coatings (Zn–Ni with 10 wt.% Ni (ZN) or Zn–Co with 3 wt.% Co (ZC), respectively) and a top ZrO2 sol–gel layer. Surface morphology peculiarities and anti-corrosion characteristics were examined using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX), atomic force microscopy (AFM), water contact angle (WCA) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) analyses, potentiodynamic polarization (PDP) curves, corrosion potential (Ecorr), polarization resistance (Rp) measurements (for a prolonged period of 25 days) and open-circuit potential (OCP). The results were compared with the corrosion peculiarities of usual zinc coating. The zirconia top coatings in both systems were amorphous and dense, possessing hydrophobic nature. The experimental data revealed an increased corrosion resistance and protective ability of the ZC system in comparison to that of ZN due to its smooth, homogeneous surface and the presence of poorly crystallized oxides (ZnO and Co3O4), both later playing the role of a barrier for corrosive agents.