Binary mixtures of two novel amphiphilic mixtures of tetradecanol (TDC) and orthophosphoric acid (H3PO4) exhibit an interesting liquid crystalline phases in large range of concentration and temperature, The mixtures in the concentration range between 10 to 60% of TDC in H3PO4 exhibits SA, SD and SE phases. The mixtures with higher concentration of TDC exhibit smectic phases. X-ray, DSC, Optical and NMR studies have been carried out.