LIBS mapping was used to analyze and detect the elemental distribution of iron ore surface with self-developed software and 532 nm Nd∶YAG laser. Firstly, in order to illustrate the relationship between element content and spectral intensity, the calibration curve was established by scanning the surface of standard sample. Then, a self-made sample was homogeneously divided into three parts that was pressed by three different standard iron ore powders. For the purpose of validating the mapping technology, a two-dimensional concentration distribution profile was generated after scanning the sample surface which was compared with surface morphology phase of the sample. Finally, with the resolution of 100 microns, the surface scanning analysis of the natural iron ore within the scope of 14 mm×11 mm was implemented. With this basis, the distribution profile of the elements Ca, Al, Ti and Mn were obtained, and the analysis results were compared with the surface morphology phase of the natural iron ore. The results showed that LIBS mapping technology could be used to achieve the qualitative analysis of component gradient distribution of the heterogeneous sample surface.