The presence of gold on the sidewall of a tapered, single silicon nanowire is directly quantified from core-level nanospectra using energy-filtered photoelectron emission microscopy. The uniform island-type partial coverage of gold determined as 0.42+/-0.06 (approximately 1.8 ML) is in quantitative agreement with the diameter reduction of the gold catalyst observed by scanning electron microscopy and is confirmed by a splitting of the photothresholds collected from the sidewall, from which characteristic local work functions are extracted using a model of the full secondary electron distributions.