Metalorganic chemical vapor deposition (MOCVD) has been used for development of photovoltaic (PV) structures that enable enhanced efficiency for triple-junction solar cell (TJSC) devices. The in-plane strain, lattice match, surface defects, surface morphology, compositional uniformity, threading dislocations (TDs), and depth profile of each layer of the TJSC structure have been examined. The heteroepitaxial layers were found to be near lattice matched to the substrate with excellent coherence between the layers. The analysis explained that the indium gallium phosphide (InGaP) and indium gallium arsenide (InGaAs) layers on germanium (Ge) substrate are a strained structure with purely tetragonal crystalline phase, which indicates that the TJSC structural layers could maintain high crystalline quality. The biaxial in-plane strain in each layer of the TJSC structure is compressive and varies in magnitude for each layer in the structure, being strongly influenced by the Ge substrate and the multiple epilayers of the PV structure. Transmission electron microscopy (TEM) results show no TDs observed over a region with area of 500 nm2, with surface defect density less than 1 × 108 cm−2. No evidence of stacking faults and no visible defects of antiphase domains (APDs) at interfaces were observed, indicating adequate nucleation of epitaxial layers on the substrate and on subsequent growth layers. Furthermore, secondary-ion mass spectrometry (SIMS) analysis showed no significant Ge diffusion from the substrate into the TJSC structure.