In this Article, we demonstrate the dependence of the lifetime of a volatile droplet on the hydrophobicity of the substrate. Ethanol droplets placed on the molecularly smooth surfaces of three polymers, applied to substrates by spin-coating, showed distinct types of behavior depending on the hydrophobicity of the latter. High contact angles, theta, lead to fairly regular recession of the triple line during liquid evaporation at essentially constant theta, whereas low contact angle caused pinning, theta decreasing with time. The latter case leads to shorter drop lifetimes.