Developing molecular self-assembly is an important step to generate ordered nanostructure materials. In this pursuit, a simple template-free method is reported to develop anisotropic nanostructures using metallopolymer precursors. The phenanthroline-based ruthenium complex monomer (PDAR) and its polymers [3-armed PPDAR (PPDAR-3) and 4-armed PPDAR (PPDAR-4)] were synthesized using ATRP method. These materials displayed higher glass transition temperatures (182 °C for PPDAR-4 and 176 °C for PPDAR-3) compared to the linear polymer, PPDAR (144 °C). The materials showed metal-to-ligand charge transfer (MLCT) absorption peak at 440 nm and armed polymers exhibited higher molar absorption coefficient (PPDAR-4: 7.6 × 105 M−1 cm−1 and PPDAR-3: 6.58 × 105 M−1cm−1) compared to the linear polymer (4.6 × 105 M−1cm−1). The materials were self-assembled in the presence of non-polar solvents to form uniform nano-domain micelles. Thin films of these materials were formed and subjected to elevated annealing temperatures (180 °C) and were fully characterized by AFM, SEM, and XRD techniques to understand the mechanism of self-assembly. Furthermore, dye sensitized solar cell (DSSC) devices were fabricated using the materials as additional components of a liquid electrolyte (I3−/I−) to explore the role of these architectures on open circuit voltage (VOC) as well as cell power conversion efficiency (PCE). Overall, this study provides new insights in the area of metallopolymers.Read less <