The computer simulation of H(3)PO(4)-N,N-dimethylformamide (DMF) mixtures over the whole concentration range using molecular dynamic (MD) methods has been carried out. The preferential orientations of the nearest neighbors of H(3)PO(4) and DMF molecules were obtained using the ranked radial distribution functions technique. On the basis of MD results, the parameters of hydrogen bonds between molecules in mixture were calculated. The changes of the intermolecular structure of mixture as a function of acid composition over the whole concentration range were analyzed and reported. Analysis of O···H distance distributions and angles between O-H (H(3)PO(4)) and C=O (DMF) or P=O (H(3)PO(4)) vector distributions showed that O(DMF) and O(H(3)PO(4)) may each have two hydrogen bonds.