A photoelectron spectrum of H2O has been recorded at a resolution of 2 meV under Doppler-free conditions. Complex rotational structures appear in the individual vibrational states of the electronic (X) over tilde (+) B-2(1) and (A) over tilde (+) (2)A(2) states in H2O+. The rotational structures are analyzed and well reproduced using a spectator orbital model developed for rotationally resolved photoelectron spectroscopy.