Poly (3, 4-ethyleendioxythiophene) (PEDOT) coated titanium dioxide (TiO2) nanoparticles were prepared through a soft chemistry approach-assisted in situ synthesis route. The as synthesized PEDOT/TiO2 nanocomposites (NCs) are characterized by XRD, Raman, BET, XPS, SEM, TEM and EDX analysis/elemental mapping. The formation mechanism of PEDOT/TiO2 NCs is also illustrated. The uniformly TiO2 nanoparticles dispersed in PEDOT matrix improving the electrochemical performance of the ternary PEDOT/TiO2/sulfur composite, which exhibits higher reversible capacity and better rate capability compared with the PEDOT/S and TiO2/S composites. The reversible capacity of PEDOT/TiO2 NCs can be up to 1110mAhg−1 and was retained 532.1mAhg−1 after 500 charge-discharge cycles at the rate of 1C, which confirms the good cycling behavior. The superior electrochemical performance of the PEDOT/TiO2 NCs could be attributed to the uniform conducting polymer layer and improving the electrical conductivity of TiO2, the lower charge-transfer resistance and larger lithium ion diffusion coefficient.