Titanium diboride has been synthesised from NaCl-KCl-NaF-K2TiF6-KBF4 molten system at 700°C on W cathode by DC and PCR techniques in the wide range of current densities. From comparison of Equilibrium Electrochemical Synthesis (EES) diagrams and linear voltammograms the conclusion was made, that first a thin layer of W2B will be formed, with further growth of TiB2. Deposits were analysed by X-ray diffractometry, SEM and GDOES. These techniques confirmed the validity of theoretical predictions. Finer structure has been obtained by the PCR technique compared to the DC technique. Titanium and boron atoms were found to diffuse deep into the tungsten substrate with a constant ratio of 1:2.