High thermally and thermo-oxidatively stable poly(phenylene-carborane) (PPB) was synthesized via Ni(0)-catalyzed polymerization of bis(aryl chloride) monomer containing carborane. This polymer was soluble in THF and NMP at room temperature, thus allowing molecular weight and spectroscopic analysis. Number-average molecular weight determined by ¹H-NMR spectroscopy was 5.4 × 10³ g/mol. The crystalline character of PPB was verified by XRD analysis. This polymer exhibited excellent thermal and thermo-oxidative stability with 5% weight loss temperature to be 707 °C and >1000 °C in nitrogen and air, respectively. High char yields of 93.2% and 97.9% were obtained at 1000 °C in nitrogen and air, respectively. Additionally, PPB has proven to be excellent sing-source precursor to boron-carbide/carbon ceramic materials with high ceramic yields in the range of 91.1%–92.6%. According to XRD analysis, boron carbide crystallization for PPB occurred between 1000 and 1200 °C.