A nanoparticle-imprinted matrix was formed by electrodeposition of poly-plumbagin around silica template nanoparticles supported on a glassy carbon electrode. Different functional groups are introduced to the matrix by conjugate addition of bifunctional thiols to tune the selectivity of the system. Upon removal of the template nanoparticles, the cavities selectively capture citrate-modified gold analyte nanoparticles in dependence on the introduced functionality, the pH and the size of the nanoparticles.