The photophysical and photoelectrochemical properties of first- and second-generation dendrimers with ruthenium tris-bipyridine peripheral groups and a tri-viologen like core (RU(3)A(3) and RU6V3) were investigated in solution and when embedded within assembled films. The stepwise assembly of these dendrimers on quartz and ITO surfaces utilizing the layer-by-layer approach was investigated. The amount of the assembled dendrimers was found to increase on going to the higher generation dendrimer. This dendrimer generation effect was evident from the UV-vis, atomic force microscopy, and electrochemical measurements of the dendrimers in either solution phase or when embedded in films. The anodic and cathodic photocurrent generation was seen upon visible light irradiation, with higher photocurrents for RU6V3 than RU(3)A(3). This observation was attributed to better light-harvesting properties, thicker films, and slower charge recombination processes in RU6V3 when compared to RU(3)A(3).