Films of Pt, Pd, Rh, and Re with metal volume fractions of 0.3 to 0.5 have been prepared by mass-transport-limited photoelectrodeposition onto (001) p-InP photocathodes from ∼5 × 10−5 M solutions of the metal ions in 1 M HClO4. These films exhibit their normal catalytic activities (e.g., in hydrogen evolution) and have normal crystal structures, yet are substantially more transparent than equivalent dense films of the same metal loading per unit area. Effective-medium analysis of the spectroellipsometrically measured dielectric functions of these films shows that the anomalous transparency is due to microstructure: depolarization factors and metal packing fractions obtained by best-fit model calculations indicate dendritic (Rh), particulate (Pt, Pd), or platelet (Re) forms that are poorly interconnected in directions parallel to the surface, and whose dimensions are all small compared to the wavelength of light. Transmission electron micrographs confirm these results and reveal that these films consist of primary building blocks of ca. 5 nm crystallites that are organized into relatively loosely packed secondary structures. Potential applications of these films include the formation of efficient metallic-catalyst-coated photoelectrodes on poor-quality semiconductors.