Residual water vapour present in the vacuum system has been observed to play a dominant oxidising role in the 250 keV D+ induced radiolysis of polyimide (Kapton-H). The partial pressure (pp) of water in the vacuum system decreases sharply as the D+ beam impinges the polymeric surface, but soon after, it recovers to its initial value as the accumulated dose increases. Emission of CO2 is observed which has its maximum at a time when the H2O partial pressure is at a minimum. The CO2 level also returns to its original level with time. This complementary variation of CO2 and H2O confirms that absorbed and adsorbed water molecules are radiolysed by the ion beam and initiate oxidation of the radiolytically evolved CO to yield CO2 on and within the ion implanted surface of the polyimide. Further, the small enhancement in the 28 amu peak (N2 + CO), which exhibits no maximum/minimum over the entire implantation time, can be understood in terms of the evolution of N2 from the imide ring as a result of radiolysis of this nitrogen containing polymers.