Optimization of negative ion sources operated with deuterium may be limited by the lack of data on fundamental processes. Insight can be obtained from studies focusing on a direct comparison of "H" _"2" and "D" _"2" plasmas. Herein, the ECR volume negative ion source Prometheus I is operated with both "H" _"2" and "D" _"2" gases and the properties of the generated plasmas are probed by means of electrostatic probes and laser induced photodetachment. A parametric study, involving pressure and microwave (2.45 GHz) power variation, reveals similar qualitative trends for most of the plasma properties in both gases. However, quantitavely, differences do exist for the plasma potential, the cold electron density and temperature, and the negative ion to electron density ratio. The hot electron population density and temperature are similar in both plasmas. EEDFs are thus isotope dependent at the lower energies in the ECR–heated plasmas, suggesting an effect that has been meagerly considered in the literature either experimentally or numerically. Overall, nearly the same maximal "H" ^"_" and "D" ^"_" negative ion densities are achieved (i.e., "4×" 〖"10" 〗^"9" " " 〖"cm" 〗^"-3" ). The results are eventually elucidated according to the ECR heating mechanisms and the production/destruction paths of the negative ions.