MoB/CoCr, a novel thermal spray material, with high durability in molten Al and/or Al-Zn alloys has been developed to utilize for die casting parts of Al alloy, and for hot continuous dipping roll in Zn and Al-Zn plating lines. The durability of the MoB/CoCr coatings prepared by high velocity oxy-fuel (HVOF) spraying has been investigated using a molten metal immersion tester. The immersion tests revealed that the MoB/CoCr coating has much higher durability without dissolution in the Al alloys than conventional spray coatings, such as WC/12%Co and WC/10%Co/4%Cr, as well as various other surface modification methods. The MoB/CoCr coating also has showed higher durability in the molten Al-Zn alloy when the coefficient of thermal expansion (CTE) of the substrate is similar to that of the MoB/CoCr. The lifetime of the coating on stainless 316L substrate, widely used as the hot continuous dipping roll, was insufficient because of the generation of cracks due to a large difference in the CTE between the MoB/CoCr coating and substrate. Basic anneal examinations have revealed that optimization of coating structure by changing undercoat material and its thickness is effective to improve the lifetime.