A system mingw-w64 gcc installation has many many libs in /mingw64/$triple/lib which gcc will make available for linking by default. The bundled GCC that rust provides, however, does not link against these libraries by default (they are not in any -L flag). This means that gcc invocations which would otherwise work on the system begin to fail because the bundled GCC is preferred.
For a concrete example, see rust-lang/cargo#620.
cc @vadimcn