The exact quantification of surface-attached initiators for grafting-from radical polymerization on micro- and nanoparticles is still a challenging task. Here we demonstrate that, by combining UV/vis spectroscopy and an efficient derivatization protocol, the originally nearly invisible ATRP initiators and RAFT chain transfer agent entities can be quantified easily and precisely. Application of an isorefractive dispersion medium for the nanoparticles moreover provides reliable information about the amount of chemically really "accessible" surface-grafted initiators, that is, those that are not hidden in the particle's shell interior. To qualify the developed procedure further, nanoparticles of different grafting densities were generated, and the values determined afterward for the initiator concentration were in good agreement with expectations.