Photoelectrochemical cells based on traditional and nanostructured ZnO thin films are investigated for hydrogen generation from water splitting. The ZnO thin films are fabricated using three different deposition geometries: normal pulsed laser deposition, pulsed laser oblique‐angle deposition, and electron‐beam glancing‐angle deposition. The nanostructured films are characterized by scanning electron microscopy, X‐ray diffraction, UV‐vis spectroscopy and photoelectrochemical techniques. Normal pulsed laser deposition produces dense thin films with ca. 200 nm grain sizes, while oblique‐angle deposition produces nanoplatelets with a fishscale morphology and individual features measuring ca. 900 by 450 nm on average. In contrast, glancing‐angle deposition generates a highly porous, interconnected network of spherical nanoparticles of 15–40 nm diameter. Mott‐Schottky plots show the flat band potential of pulsed laser deposition, oblique‐angle deposition, and glancing‐angle deposition samples to be −0.29, −0.28 and +0.20 V, respectively. Generation of photocurrent is observed at anodic potentials and no limiting photocurrents were observed with applied potentials up to 1.3 V for all photoelectrochemical cells. The effective photon‐to‐hydrogen efficiency is found to be 0.1%, 0.2% and 0.6% for pulsed laser deposition, oblique‐angle deposition and glancing‐angle deposition samples, respectively. The photoelectrochemical properties of the three types of films are understood to be a function of porosity, crystal defect concentration, charge transport properties and space charge layer characteristics. Three types of ZnO photoelectrochemical cell are examined and utilized for water splitting. Pulsed laser deposition, oblique angle deposition and glancing angle deposition techniques are found to drastically affect crystal growth, morphology and photoelectrochemical properties. Hydrogen generation efficiencies are 0.1, 0.2 and 0.6% for pulsed laser deposition, oblique angle deposition and glancing angle deposition photoelectrochemical cells, respectively.