Primeiro, você precisa instalar o "gcc-multilib" e o "g ++ - multilib"
sudo apt-get install gcc-multilib g++-multilib
Então seu comando atual funcionará,
$ cat hello.c
#include <stdio.h>
int main(int argc, char *argv[]) {
puts("Hello, World!");
}
$ uname -a
Linux vbox-1404 3.13.0-24-generic #46-Ubuntu SMP Thu Apr 10 19:11:08 UTC 2014 x86_64 x86_64 x86_64 GNU/Linux
$ gcc -m32 hello.c
$ ./a.out
Hello, World!
$ file a.out
a.out: ELF 32-bit LSB executable, Intel 80386, version 1 (SYSV), dynamically linked (uses shared libs), for GNU/Linux 2.6.24, BuildID[sha1]=80bdc95e2941e3ba8d7bb7c1682098f20e77cebc, not stripped