Laser Chemical Vapor Deposition (LCVD) is an additive process in which freestanding fibers are deposited by the thermal dissociation of a precursor gas-to-solid form under a translating laser focal point. By altering gas type, laser power, growth speed, and chamber pressure, LCVD offers a substantial processing space in tailoring fiber microstructures. Using different hydrocarbon precursors, i.e., methane (CH4), ethane (C2H6), ethylene (C2H4), and propane (C3H8), various growth regimes are identified which include surface kinetic limited, mass transport limited, and gas phase nucleation, with each regime promoting a different fiber microstructure. These differences are explained by the type of bond structure (single, double, triple) and available carbon per molecule for deposition. Using this information, a series of TiC fibers were then grown by reacting the hydrocarbon precursor with TiCl4. The results of which reveal the ability to create single to core shell fibers dependent upon the reaction temperature and hydrocarbon precursor.