We present an experimental and theoretical study of the electromagnetic interaction between a single gold nanoparticle and a thin gold substrate separated by a sub-50 nm-thick optically absorptive polythiophene spacer layer. Single-particle dark-field scattering spectra show distinct resonance features assigned to four different modes: a horizontal image dipole coupling mode, a vertical image dipole coupling mode and horizontal and vertical coupling modes between localized surface plasmon resonances (LSPRs) and surface plasmon polaritons (SPPs). Relatively broadband spectral tuning of the modes can be achieved by modification of the thickness of either the absorptive spacer or the underlying metal film. Dark-field images also reveal the existence of particles for which the signal of the horizontal image dipole coupling mode is suppressed. This is attributed to partial-embedding of gold nanoparticles into the polythiophene spacer and leads to higher scattered light intensities at longer wavelengths. Full-field electromagnetic simulations show good agreement with the experimental results for the various sample conditions. Strong local electric field confinement at longer wavelengths in the polythiophene spacer, due to the vertical image dipole coupling mode and a LSPR–SPP coupling mode, is also observed in simulations and contributes to absorption enhancement in the spacer. Furthermore, we find absorption enhancement in the semiconducting polythiophene spacer increases with decreasing thickness, indicating the increased light trapping ability of the gold nanoparticles for ultra-thin semiconductor layers. The need for ever-thinner semiconductor layers in optoelectronic devices requires effective light trapping at deeply-subwavelength scales. This work demonstrates that light trapping in sub-50 nm-thick semiconductor layers is possible using a “sphere-on-plane” system and offers insight into how coupling modes can be manipulated in this system.