The location and morphology of femtoliter nanodroplets that nucleate and grow on a microcap-decorated substrate in contact with a liquid phase were investigated. We experimentally examined four different wetting combinations of the flat area and the microcaps. The results show that depending on the relative wettability, the droplets sit either on the plain surface or on the top of the microcap or on the rim of the microcap. The contact angle and, for the last case, the radial positions of the nanodroplets relative to the microcap center were characterized, in reasonable agreement with our theoretical analysis, which is based on an interfacial energy minimization argument. However, the experimental data show considerable scatter around the theoretical equilibrium curves, reflecting pinning and thus nonequilibrium effects. We also provide the theoretical phase diagram in parameter space of the contact angles, revealing under which conditions the nanodroplet will nucleate on the rim of the microcap.