4Al(s) + 3O2(g) —> 2Al2O3(s)
First, write out the unbalanced equation.
Al(s) + O2(g) —> Al2O3(s)
Balance the oxygens first. What do you need to multiply by to get to a common multiple of 2 and 3 to balance the oxygens? The common multiple is 6, so multiply the O2 by 3 and the Al2O3 by 2.
Al(s) + 3O2(g) —> 2Al2O3(s)
Now balance your aluminum. You have 1 in the reactants and 4 in the products, so multiply the reactant by 4.
4Al(s) + 3O2(g) —> 2Al2O3(s)
Hope this makes sense!