tl;dr GCC does not reorder struct members.
GCC is smarter than most of us in producing machine code from our source code; however, I shiver if it was smarter than us in re-arranging our structs, since it's data that e.g. can be written to a file. A struct that starts with 4 chars and then has a 4 byte integer would be useless if read on another system where GCC decided that it should re-arrange the struct members.