This is pure memory recall ( << is the disclaimer)
Enamel is a very hard yet very brittle material. While it may be good at holding its shape when grinding against softer material, it may not be very good at load bearing, and since its a dynamic load (living being weight) it can't really stay in compression like how concrete holds up bridges and whatnot. For example if you compress a column of enamel vertically, it may be ok but if you suddenly hit the side and it snaps because of a lateral force and its brittleness, it won't do.
I'd suggest some things like normal terrestrial bone (like bird or mammal bone) but that'd be boring.
Even though titanium is often used in bone replacement, its biostable so it can't be naturally made into bone by an animal. Shame, it is light and durable, a great bone material. (aka the body can't use or move titanium and so can't do anything about it naturally)
Avatar did mention carbon-fiber bone and I suppose that is plausible considering that bodies do manipulate carbon in some form, with some furious hand-waving.
This is probably going to be a no go but keratin and chitin seem promising as a bone material: it is light, durable, and flexible (maybe keratin is a little too flexible but chitin is used in crustaceans and insects. Insects especially used to be huge in the prehistoric times, iirc.