The ultimate goal of nanotechnology is to design successful syntheses to produce nanomaterials with required properties. The properties of nanoparticles mainly depend on their size, shape and crystal structure, hence control over these factors is a major issue in this field. In this study, Co nanoparticles with four different crystallographic structures (hcp, fcc, bcc and epsilon) have been wet-chemically synthesized by varying precursors and surfactants in the reaction. Co K-edge absorption spectra were collected in transmission mode at the XMP beamline at the Center for Advanced Microstructures and Devices (CAMD). The X-ray Absorption Near Edge Structure (XANES) and Fourier Transformed Extended X-ray Absorption Fine Structure (FT EXAFS) spectra were analyzed using the “fingerprint method”, i.e. by comparing them with either standard compounds or with the simulated spectra that were calculated using the FEFF8 code. EXAFS spectra were also analyzed by fitting them with relevant crystallographic models in r-space including higher coordination shells using the IFEFFIT analysis program. All four crystal structure types were conclusively determined by using this approach.