Existing inorganic materials for radiation sensors suffer from several drawbacks, including their inability to cover large curved areas, lack of tissue-equivalence, toxicity, and mechanical inflexibility. As an alternative to inorganics, poly(triarylamine) (PTAA) diodes have been evaluated for their suitability for detecting radiation via the direct creation of X-ray induced photocurrents. A single layer of PTAA is deposited on indium tin oxide (ITO) substrates, with top electrodes selected from Al, Au, Ni, and Pd. The choice of metal electrode has a pronounced effect on the performance of the device; there is a direct correlation between the diode rectification factor and the metal-PTAA barrier height. A diode with an Al contact shows the highest quality of rectifying junction, and it produces a high X-ray photocurrent (several nA) that is stable during continuous exposure to 50 kV Mo Kalpha X-radiation over long time scales, combined with a high signal-to-noise ratio with fast response times of less than 0.25 s. Diodes with a low band gap, 'Ohmic' contact, such as ITO/PTAA/Au, show a slow transient response. This result can be explained by the build-up of space charge at the metal-PTAA interface, caused by a high level of charge injection due to X-ray-induced carriers. These data provide new insights into the optimum selection of metals for Schottky contacts on organic materials, with wider applications in light sensors and photovoltaic devices.