No, you can't have that. It is consistent that the real numbers are a countable union of countable sets, in which case you immediately have that there is no nontrivial measure which is countably additive on the real numbers.

There are other models, however, in which $\aleph_1$ is singular, the countable union of countable sets of real numbers is countable; but every set is Borel. In such models, I believe, you can't have a countably additive Lebesgue measure as well.