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An algorithm for fitting with Least Square is a traditional and an effective method in processing with experimental data. Due to the lack of definite representation, it is difficult to fit measured data with free curves or surfaces. B-Spline is usefully utilized to express free curves and surfaces with a few parameters. This paper presents the combination of these two techniques to process the point data measured from CMM and other similar instruments. This research shows tests and comparison of the simulation results from two techniques.