The determination of the orientation and molecular density for several porphyrin dyes adsorbed on planar TiO2 surfaces using X-ray reflectometry (XRR) is reported. Adsorption of nanoscale water layers occurred rapidly upon exposure of freshly prepared TiO2 surfaces to ambient conditions; however, this was successfully eliminated, resulting in clearly discernible adsorbed dye layers for sensitized surfaces. Adsorbed dye orientations, determined from computations constrained by the measured dye layer thickness, were calculated to have a binding tilt angle of 35°-40°. Combining the XXR data with the orientation models indicates that the porphyrins form densely packed surfaces with an intermolecular spacing of 3-4 Å, consistent with π-π stacking interactions. Changes in the molecular size of probe dyes were reflected in corresponding changes in the measured dye layer thickness, confirming the ability of this technique to resolve small variations in dye layer thickness and consequently adsorption orientation. Application of these results to understanding the behavior of dye-sensitized devices is discussed. © 2011 American Chemical Society.