On the basis of fundamental parameter approaches, the validity of standardless wavelength dispersive X‐ray fluorescence (WDXRF) and X‐ray powder diffraction algorithms was confirmed for analyzing Egyptian iron ore samples collected from two different locations, Aswan and Baharyia. The studied Egyptian iron ores represent different depositional environments and consequently exhibit variable mineralogical and chemical compositions. In the case of WDXRF analysis, the ground powders of iron ore samples were mixed and pressed with low contamination binder in a mass ratio of wax: sample = 4: 0.9 g at 120 kN cm−2. A standardless method for quantitative WDXRF was employed, which requires accurate determination of the amount of organic material in the sample. On the basis of differential thermal analysis, a new method is introduced for the determination of loss of ignition. With the application of the proposed method and standardless quantitative analysis, results for 12 elements in iron ores were obtained: Fe, Mn, Mg, Si, Al, Ca, Na, K, S, Ba, Zn, and Cl. The reliability and precision of the adopted procedure were tested against a standard reference material ‘Iron ore concentrate (SRM 690, NIST, USA)’. The quantitative analysis results of the certified reference material were found acceptable. Depending on the WDXRF results, the powder samples were directly introduced to X‐ray powder diffraction goniometry, and the phase compositions were quantitatively determined by using a standardless analysis program based on Rietveld method. The main phases of all iron ore samples are the hematite and goethite, whereas other phases are found with varying ratios, namely quartz, nordstrandite, rhodochrosite, kaolinite, todorokit, bassanit, andydrite, and hydroxyapatite. Copyright © 2012 John Wiley & Sons, Ltd.