The morphological evolution of Ge layers growing on the SiO2/Si(100) substrate by photo-excited chemical vapor deposition was traced through an analysis of pseudodielectric functions measured by real-time spectroscopic ellipsometry. Simulation and fitting were carried out on multiple samples with various Ge film thicknesses as well as on sequential optical spectra from a sample with an incremental buildup of Ge atoms on one substrate. Single- and two-layer models involving crystalline Ge ( c-Ge), amorphous Ge ( a-Ge), and void components were employed under the Bruggeman effective medium approximation to represent wetting of the SiO2 surface, nucleation of Ge seeds for the subsequent dot/island formation, and steady-state dot/island growth. A combination of c-Ge and a-Ge represents intermediate crystallinity, and void represents vacant space between dots/islands. A single-layer model with a mixture of c-Ge, a-Ge, and void components was used for crude estimation of the composition from which the time evolution of the volume fraction of the components was derived. However, fitting in the early growth stage resulted in an unrealistic structure, indicating that the dielectric function of the thin hydrogenated Ge network layer was very different from those of c-Ge and a-Ge. The optical spectra of dots/islands at the intermediate growth stage could be reproduced by a two-layer model consisting of a ( a-Ge + void) layer overlaid on a ( c-Ge + void) base layer. The real-time Ψ–Δ trajectories of ellipsometric angles monitored at a photon energy of 3.4 eV consisted of three branches. They could be reproduced by assuming the growth of an outer layer with an appropriate composition. After wetting on SiO2 (branch 1), the Ge seed layer nucleates while the volume fraction of Ge rapidly decreases from 70% to 25% with proceeding growth (branch 2). Then, the volume fraction of Ge continuously increases up to 65%, eventually reaching steady-state dots/island growth (branch 3)