Zirconium carbide (ZrC) was synthesized by polycondensation and carbothermal reduction reactions from an organic–inorganic hybrid complex. A natural biopolymer Gum Karaya (GK) and zirconyl oxychloride octahydrate (ZOO) were used as the sources of carbon and zirconium, respectively. FTIR of as-synthesized dried complexes revealed formation of Zr–O. Pyrolysis of the complexes at 1200°C/1 h under argon resulted in tetragonal and monoclinic zirconia which after heat treatment at 1400°C–1550°C transformed to zirconium carbide. Thermal analysis shows that the GK–ZOO complexes lost less mass than the pristine GK to 600°C. The intensity of exothermic decomposition decreases and shifted to higher temperature for the hybrid complexes indicating that zirconia induced thermal stability. A maximum ZrC yield of ~60 wt% is obtained for the intermediate GK–ZOO ratio of 1:2. Particles pyrolyzed for 1 h at 1550°C were coarser (5–10 μm) with flakes for lower GK–ZOO weight ratio, but were spheroidal with narrow size distribution (~1 μm) with increasing GK–ZOO weight ratio.