The unbalanced equation is:
Fe(s) + O2(g) —> Fe2O3(s)
To balance oxygens, multiply O2 by 3 and Fe2O3 by 2.
Fe(s) + 3O2(g) —> 2Fe2O3(s)
Balance your iron by multiplying Fe by 4, since you have 4 Fe in the products now.
4Fe(s) + 3O2(g) —> 2Fe2O3(s)