We demonstrate the spatial separation of pyrrole and pyrrole(H2O) clusters from the other atomic and molecular species in a supersonically-expanded beam of pyrrole and traces of water seeded in high-pressure helium gas. The experimental results are quantitatively supported by simulations. The obtained pyrrole(H2O) cluster beam has a purity of similar to 100%. The extracted rotational temperature of pyrrole and pyrrole(H2O) from the original supersonic expansion is T-rot = 0.8 +/- 0.2 K, whereas the temperature of the deflected, pure-pyrrole(H2O) part of the molecular beam corresponds to T-rot approximate to 0.4 K.