Even though EDXRF analysis has major advantages in the analysis of stainless steel samples such as simultaneous determination of the minor elements, analysis can be done without sample preparation and non-destructive analysis, the matrix issue arised from the inter element interaction can make the the final quantitative result to be in accurate. The paper relates a comparative quantitative analysis using standard and standardless methods in the determination of these elements. Standard method was done by plotting regression calibration graphs of the interested elements using BCS certified stainless steel standards. Different calibration plots were developed based on the available certified standards and these stainless steel grades include low alloy steel, austentic, ferritic and high speed. The standardless method on the other hand uses a mathematical modelling with matrix effect correction derived from Lucas-Tooth and Price model. Further
improvement on the accuracy of the standardless method was done by inclusion of pure elements into the development of the model. Discrepancy tests were then carried out for these quantitative methods on different certified samples and the results show that the high speed method is most reliable for determining of Ni and the standardless method for Mn.