Investigation of Fe K-edge X-Ray Absorption Near Edge Spectroscopy (XANES) spectra of Fe3O4 (FeO.Fe2O3) from natural source compared with the Fe3O4 standard is presented. The natural Fe3O4 powder was prepared from ironstone of Tanah Laut, Kalimantan Selatan by co-precipitation method. XANES measurements in transmission mode were performed at the Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima, Thailand. XRD phase analysis confirms that the synthesized Fe3O4 powder is a single phase, but it cannot determine the proportion of Fe2O3 and FeO in the structure. TEM measurement confirms that the particle size of natural Fe3O4 about 10 nm. Qualitative analysis of the pre-edge XANES data revealed that the absorbing atom in the XAS measurement is Fe3+. Meanwhile, the absorption edge (E0) values of natural and standard Fe3O4 powders were 7126.44 eV and 7125.02 eV, respectively. The proportion was then acquired using XANES data analysis through Linear Combination Fitting (LCF). It was found that the natural Fe3O4 sample consisted of 98 wt. % Fe2O3 and 2 wt.% FeO, while the standard Fe3O4 powder consisted of 96 wt. % Fe2O3 and 4 wt. % FeO. The mechanism of the absorption in both samples is also described and compared.