The invention provides a novel coating composition which includes: (a) a polyester-based resin component, (b) an epoxy component, (c) a cross-linker component, (d) a catalyst component, and (e) a diluent component. The polyester-based resin component includes at least one phosphatized polyester resin; and the epoxy component includes at least one phosphatized epoxy resin. These coating compositions are particularly suitable as primers, and especially as primers for use used in conjunction with coating composition which include fluorocarbon polymers. Also provided is a method of providing a substrate with a multilayer coating system. This method includes: (a) applying at least one layer of the aforementioned novel primer onto a substrate; and (b) applying at least one layer of a second coating composition over the primed substrate of step (a). When this method employs the use of a second coating composition which includes fluorocarbon polymers, the result is multi-layered coated substrate which, while having excellent weatherability properties, also has excellent formability properties.