Charge transport across a self-assembled monolayer (SAM) can involve either individual molecules only (throughbond model) or also intermolecular pathways (through-film model or matrix effects). In this context, we test a possible involvement of the latter pathways in the electron transfer (ET) across a model, nitrile-terminated naphthalene-2-thiolate (NC-Nap) SAM on Au(111). For this purpose, we apply the so-called core-holeclock approach in the framework of resonant Auger electron spectroscopy, allowing the measurement of the characteristic ET time from the nitrile tail group of NC-Nap to the substrate. The efficiency of possible intermolecular pathways depends on the electronic coupling between individual NC-Nap molecules, which was progressively reduced by mixing NC-Nap with short-chain alkanethiolates in binary SAMs. It turns out that the value of the characteristic ET time, estimated as 24 ± 4 fs for the reference, single-component NC-Nap SAM, does not vary noticeably in the binary monolayers, independent of the NC-Nap content. This means that the matrix effects play a negligible role for ET dynamics in the given model SAM, strongly favoring the through-bond CT model.