A technique is presented of restoring the electronic density of states of the valence band from data of X-ray photoelectron spectroscopy (XPS). The originality of the technique consists in using a stochastic procedure to solve an integral equation relating the density of states and the experimental X-ray photoelectron spectra via the broadening function. To obtain the broadening function, only the XPS spectra of the core levels are needed. The results are presented for bulk sample of gold and tungsten and nanoclusters of tantalum; the possibility of using the results to determine the density of states of low-dimensional structures, including ensembles of metal nanoclusters, is demonstrated.