Did Calvin and Luther believe in free will? According to the Roman Catholic Church, man’s will is in no way determined but that man has the self-power to will good or evil toward God. 

Now it seems that Calvin and Luther didn't agree with that. Because mankind was due to the sin of Adam totally corrupted. Does this mean that free will didn't exist for them?
Yes Luther denied we had the ability to choose to respond affirmatively to the Gospel and so save ourselves. He held that it was only through God's intervention that we could be saved. God had to convert a person through the Word, by means of the Holy Spirit changing our hearts and leading us to embrace Christ as our Saviour, in order for us to be saved. This wasn't something in our power to achieve since we had been corrupted by the sin of our first parents and could only reject the Gospel and oppose God. Also in order to be saved God must first elect to save us from eternity and predestine us to believe. This was Luther's position as found in his book “The Bondage of the Will”. Luther also explained his position in his Table Talk where for instance he says:


  Ah, Lord God! why should be boast of our free-will, as if it were able to do anything ever so small, in divine and spiritual matters? when we consider what horrible miseries the devil has brought upon us through sin, we might shame ourselves to death. For, first, free-will led us into original sin, and brought death upon us: afterwards, upon sin followed not only death, but all manner of mischiefs, as we daily find in the world, murder, lying, deceiving, stealing, and other evils, so that no man is safe the twinkling of an eye, in body or goods, but always stands in danger. And, besides these evils, is afflicted with yet a greater, as is noted in the gospel—namely, that he is possessed of the devil, who makes him mad and raging. We know not rightly what we become after the fall of our first parents; what from our mothers we have brought with us. For we have altogether, a confounded, corrupt, and poisoned nature, both in body and soul; throughout the whole of man is nothing that is good. This is my absolute opinion: he that will maintain that man’s free-will is able to do or work anything in spiritual cases be they never so small, denies Christ. This I have maintained in my writings, especially in those against Erasmus, one of the learnedest men in the whole world, and thereby will I remain, for I know it to be the truth, though all the world should be against it; yea, the decree of Divine Majesty must stand fast against the gates of hell… (CCLXII, Table Talk, translated by William Hazlitt)