We address the problem of X/γ-ray spectra estimation in the fields of nuclear physics. Bayesian estimation of experimental backgrounds has been studied in [1] involving splines. Since Dirichlet Processes (DP) sit on discrete measures, they provide an appealing prior for photopeaks. On the other hand, in order to tackle the complexity of experimental backgrounds, we consider a Pólya Tree Mixture (PTM) -with suitable parameters yielding distribution continuity -for which predictive densities exhibit better smoothness properties than a single Pólya Tree. Furthermore, it is easy to introduce some physical Compton line approximation formula (e.g. Klein-Nishina) in the base measure of the Pólya Tree, or some physically driven local modifications of the PTM prior parameters. As backgrounds depend on photopeaks locations, we propose a hierarchical model where the PTM is conditioned on the DP. We use a beta prior for the mixing proportion between the DP and the PTM. Energies are not directly observed due to detection devices noises which introduce a convolution of both discrete and continuous measures by an assumed gaussian kernel whose variance is an unknown linear function of energy. Thus, the proposed semiparametric model for experimental data becomes a hierarchical Pólya TreeDirichlet mixture of normal kernels. Besides, observed energies are binned in an histogram introducing additional quantification noise. The quantities of interest are usually posterior functionals of the DP mixing distribution. This implies an inverse problem which is carried out in the framework of finite stick-breaking representation. Thanks to conjugacy, draws from the posterior DP and PTM are easily obtained. The approach yields to a global peaks/background separation while offering spectrum resolution enhancement. The method is illustrated on experimental HPGe spectra.