Polarization-controlled excitation of plasmonic modes in nanometric Au particle-on-film gaps is investigated experimentally using single-particle dark-field spectroscopy. Two distinct geometries are explored: nanospheres on top of and inserted in a thin gold film. Numerical simulations reveal that the three resonances arising in the scattering spectra measured for particles on top of a film originate from highly confined gap modes at the interface. These modes feature different azimuthal characteristics, which are consistent with recent theoretical transformation optics studies. On the other hand, the scattering maxima of embedded particles are linked to dipolar modes having different orientations and damping rates. Finally, the radiation properties of the particle-film gap modes are studied through the mapping of the scattered power within different solid angle ranges. © 2012 American Chemical Society.