The variation of different intensity ratios with mean atomic number for qualitative analysis was investigated in EDXRF. Ten different samples with a mean atomic number between 4.268 and 5.786 were obtained by mixing zirconyl chloride octahydrate (Cl2OZr·8H2O) and cellulose (C6H10O5) powders. The samples were excited by 59.54 keV gamma rays emitted from a 241Am annular radioactive source with 5 Ci activity. The high purity germanium (HPGe) semiconductor detector with a resolution of 182 eV at 5.9 keV was used to detect the photons. (Icoh/2(μ/ρ)λ+Icomp/(μ/ρ)λ+(μ/ρ)λ−Δλ), (Icoh+IComp)/(μ/ρ)λ, (Icoh/2(μ/ρ)λ, IKα/Isc and IKβ/Isc intensity ratios in XRF spectrum for the assessment of information regarding the mean atomic number of the samples are studied. It has been observed that the total scattering intensity ratios can be used with high reliability in qualitative analysis for complex materials.