Concentrated solutions of polycarbosilane (PCS) are critically important for the development of continuous SiC precursor fibers, where solvent–polymer interactions govern rheology, viscoelastic stability, and spinnability. In this work, PCS solutions in two nonpolar hydrocarbon solvents with different molecular architectures as linear n-heptadecane and bicyclic decalin were systematically investigated over a wide concentration range, with emphasis on the semi-dilute entangled and concentrated regimes relevant to solution-based fiber spinning. A combined experimental approach involving steady and oscillatory rheometry and Fourier-transform infrared (FTIR) spectroscopy was used to elucidate the influence of solvent structure on solvation, viscoelastic response, microstructural organization, and local intermolecular interactions. Despite similar dilute-solution interaction parameters, the concentrated regimes exhibit pronounced solvent-dependent differences in elasticity, flow behavior. For the first time, linear heptadecane is identified as a viable and technologically promising solvent for PCS, enabling the formation of termostability homogeneous concentrated solutions with enhanced deformability. This behavior opens a realistic pathway toward a new solution-based fiber-spinning route based on elasticity-controlled processing. The results demonstrate that solvent molecular geometry governs the structure–rheology–processability relationship of concentrated PCS systems rather than solubility parameters alone, providing a new framework for solvent selection in SiC precursor fiber technologies.