Natural mineral rutile was studied as anode for photoelectrolysis of water. Both its photoelectrochemical behavior and semiconducting properties are examined in comparison with those of Fe‐doped synthetic single crystal , the latter independently studied to simulate the high impurity content existent in the mineral. The natural and synthetic Fe‐doped electrodes showed a performance comparable to that of arc‐plasma sprayed raw rutile, including a low breakdown potential. Flatband potentials and donor densities were determined from Mott‐Schottky plots and evidence for deep and shallow donors is discussed. Photoresponse measurements allowed us to verify the influence of the iron impurities on the performance of such electrodes.