Carbon nanotube (CNT) fibers were synthesized in this study under a hydrogen atmosphere using the floating-catalyst chemical vapor deposition (CVD) technique. Acetone, ferrocene, and thiophene served as the sources of carbon, catalyst, and promoter, respectively. By adjusting the amount of thiophene, the sulfur molar ratio in the CVD reactor was varied to study its impact on the morphology and composition of the CNT fibers. Raman and TEM analyses showed that the structural properties of the CNTs, especially the production of single-walled CNTs (SWCNTs) with a high Raman IG/ ID ratio of approximately 23.8, can be finely tuned by altering the sulfur content, which also affects the accumulation of spherical carbonaceous particles. Moreover, it was established that the electrical conductivity of the CNT fibers is significantly influenced by their specific components—SWCNTs, multi-walled CNTs (MWCNTs), and spherical carbonaceous particles. The ratios of these components can be adjusted by modifying the molar ratios of catalyst and promoter in the precursor mixture. Remarkably, SWCNTs with enhanced crystallinity were found to substantially improve the electrical conductivity of the CNT fibers, despite the presence of numerous spherical carbon impurities.