I'm not certain I'm looking at the correct file, but that does seem to be the case, at least on latest glibc: stat redirects to fstatat(AT_FDCWD) (https://sourceware.org/git/?p=glibc.git;a=blob;f=sysdeps/uni...), and fstatat calls a 64-bit system call and fails with EOVERFLOW if any of st_ino, st_size, st_blocks, st_atim, st_mtim, st_ctim wouldn't fit in the 32-bit struct (https://sourceware.org/git/?p=glibc.git;a=blob;f=sysdeps/uni...).
Yes, st_ino too, which means it could also break on a filesystem with large enough inode numbers. Using a 32-bit userspace nowadays seems more problematic the more I look.