Aluminium cast alloy AlSi7Mg0.3 is a lightweight metal commonly used in automotive, aeronautical and mechanical applications. It has good corrosion resistance but, under harsh operative conditions, would benefit from additional protection. In this study, a corrosion-protective multilayer coating system for AlSi7Mg0.3 based on hexafluoro-zirconated trivalent chromium coating (Zr-CrCC) and polyacrylic/siloxane-silica (PEHA-SS) coating was developed. The Zr-CrCC was formed by immersion of the substrate in a commercial conversion bath (SurTec® 650). PEHA-SS synthesis was based on organic precursors (2-ethylhexyl acrylate and [3-(methacryloyloxy)propyl]trimethoxysilane) and an inorganic precursor, tetraethyl orthosilicate. After deposition on AlSi7Mg0.3, each coating was first characterised individually, followed by the analysis of the multilayer using scanning electron microscopy and energy-dispersive X-ray spectroscopy. The adhesion of the coatings was evaluated with a cross-hatch cut test. The corrosion studies in sodium chloride solution using electrochemical impedance spectroscopy and salt spray testing showed that the multilayer system is superior to individual Zr-CrCC and PEHA-SS coatings. After 4 months in 0.1 M NaCl, the multilayer-coated samples exhibited the impedance at 10 mHz in the range of GΩ cm2, while scribed samples withstood the corrosion attack in a salt spray chamber for one week. Thus, albeit only about 100 nm thick, the Zr-CrCC deposited between the substrate and a 9-micrometre thick barrier sol-gel PEHA-SS coating acts as an active corrosion protection interlayer and contributes to the overall protectiveness of the multilayer system.