The service life of die and tool steels in contact with molten aluminium is important in the aluminium processing industry. This article describes an investigation of the efficiency of thermally sprayed Ti(Al,O)/Al₂O₃ and TiAl(O)/Al₂O₃ composite coatings in resisting aluminium soldering on H13 tool steel. The powder feedstocks for making the composite coatings were produced by high energy mechanical milling of a mixture of Al and TiO₂ powders using different molar ratios followed by a thermal reaction process. The feedstocks were then thermally sprayed using a high velocity oxygen fuel (HVOF) technique onto an H13 steel substrate to produce composite coatings. The performance of the coatings was assessed in terms of Al soldering and liquid metal corrosion resistance after immersing in molten aluminium at a temperature of 700 ± 10 °C. The results of this study showed that composite coatings have a potential to act as a physical barrier to prevent aluminium attack on H13 tool steel. The nature of Al attack on H13 tool steel changed from generalised to more localised attack with the thermally sprayed coating. A Ti(Al,O)/Al₂O₃ composite coating was not attacked by molten aluminium, however localised attack on a H13 tool steel substrate was found to be caused by molten metal penetration through defects in the coating. Composite coating TiAl(O)/Al₂O₃ was attacked by molten aluminium resulting in dissolution of the coating. Composite coatings showed significantly lower dissolution in molten aluminium compared with the uncoated H13 steel. A Ti(Al,O)/Al₂O₃ composite coating was found to be a more effective protective coating than a TiAl(O)/Al₂O₃ composite coating due its greater resistance to molten aluminium attack.