It wouldn't be any better or worse that any other combination. Don't rely on the signs of Zodiac in finding your other half of the apple. Know the person, both his or her good and bad points and see if that's the right person for you.
The opinion about this combination is divided. But I feel they will work because Leo is ruled by the royal planet Sun and Libra by Venus. Generally Libran women are great looking. So the ambitious Leo man will be happy to have a beautiful Libran woman