A metallic polypyrrole film has been formed on a p-type Si substrate by means of an anodization process. An investigation of the formed polymer/pSi Schottky diodes has been made. The polypyrrole polymer provides a good rectifying contact to the p-Si semiconductor. The current-voltage (barrier height Phi(b0) = 0.84 eV) and capacitance-voltage (Phi(b0) = 0.94 eV) characteristics of the devices are significantly improved with increasing Omega(b0) and decreasing the ideality factor (n - 1.20) after a polymer melt processing step. These values of Phi(b0) are significantly larger than those of conventional Schottky diodes. Furthermore this study shows that owing to its room temperature processing the high barrier-metallic polypyrrole/pSi structures can be useful for deep level characterisation of p-Si.