The key polynomials, defined by A. Lascoux-M.-P. Schützenberger, are characters for the Demazure modules of type A. We classify multiplicity-free key polynomials. The proof uses two combinatorial models for key polynomials. The first is due to A. Kohnert. The second is by S. Assaf-D. Searles, in terms of quasi-key polynomials. Our argument proves a sufficient condition for a quasi-key polynomial to be multiplicity-free.