Pure, highly chlorinated polyvinyl chloride (CPVC), with a 63 wt % of chlorine, showed a unique-thermal-pyrolytic-phenomenon that meant it could be converted to carbon material through solid-phase carbonisation rather than liquid-phase carbonisation. The CPVC began to decompose at 270 °C, with a rapid loss in mass due to dehydrochlorination and novel aromatisation and polycondensation up to 400 °C. In this study, we attempted to prepare carbon fibre (CF) without oxidative stabilisation, using the aforementioned CPVC as a novel precursor. Through the processes of solution spinning and solid-state carbonisation, the spun CPVC fibre was directly converted to CF, with a carbonisation yield of 26.2 wt %. The CPVC-derived CF exhibited a relatively smooth surface; however, it still demonstrated a low mechanical performance. This was because the spun fibre was not stretched during the heat treatment. Tensile strength, Young’s modulus and elongation values of 590 ± 84 MPa, 50 ± 8 GPa, and 1.2 ± 0.2%, respectively, were obtained from the CPVC spun fibre, with an average diameter of 19.4 μm, following carbonisation at 1600 °C for 5 min.