The modal analysis of samples belonging to the zeolite-rich pyroclastic formation named “Neapolitan yellow tuff” (Central and Southern Italy) has been determined by full-profile refinement of X-ray powder diffraction (XRPD) data using a combined Rietveld–RIR method. The quantitative analysis and especially the zeolite content is a profitable source for geo-petrographic and genetic considerations and as well an essential source to assess the physical and chemical properties of the bulk material for a feasible use in industrial applications. Albeit a wealth of methods are used for the quantitative determination of zeolite content in pyroclastites they all fail for lack of accuracy as far as concerns the absolute standard deviation of the quantitative data. The outstanding outcomes achievable by using the Rietveld method make it as the most promising technique to fulfill this lack. The glass content in each sample is calculated by a combined Rietveld–RIR method in which a known amount of an internal standard is added to the mixture to rescale the Rietveld refined weight fractions into absolute values. Then, it is reasonable to designate this method as an external method according to the definition given by Hill and Howard (1987). Its counterpart is the internal method developed by Riello etal. (1995a,b). Other techniques such as the addition method and the background scattering volume calculation are developed to accomplish a further determination of the glass content. The results are compared to the values obtained from the Rietveld–RIR analysis. These experimental methods yield an over-estimation of the amorphous phase because the incoherent scattering contribution (air, absorption, sample holder, Compton scattering) is accounted for as the amorphous fraction itself. The glass content of each sample acquired from the Rietveld–RIR refinement on the “raw data” is compared to that accomplished from the refinement of incoherent scattering subtracted data. In addition, some largely used XRPD quantitative techniques such as the external standard and RIR (reference intensity ratio) and the influence of the sample loading method are accounted for in an internally consistent comparison among different procedures of analysis.