Zirconium diboride (ZrB2) is one of the most important ultrahigh temperature ceramics (UHTCs). ZrB2 precursor was synthesized with bis(cyclopentadienyl)zirconium dihydride (Cp2ZrH2) and boranedimethyl sulfide complex (BH3 center dot S(CH3)(2)). The influences of molar ratio of reactants and reaction temperature on the solubility of the as-synthesized precursors were investigated. The molecular structure of the precursor, pyrolysis behavior, and the composition of the derived ceramics were investigated by Xray photoelectron spectroscopy (XPS), Fourier Transformed Infrared Spectroscopy (FT IR), Raman Spectroscopy (RMS), H-1 Nuclear Magnetic Resonance Spectroscopy (H-1 NMR), B-11 Nuclear Magnetic Resonance Spectroscopy (B-11 NMR), Thermogravimetric-Mass Spectroscopy (TG-MS), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM), respectively. The results showed that, the precursor was an oligomer based on Zr-H-B polycentric bridge bonds with molecular weight of 750 and formula as (Cp2Zr(BH4)(2))(3). The precursor would probably further polymerize under vacuum or at high temperature and lead to an insoluble polymer. The ceramic yield of the precursor at 1000 degrees C was around 66% under Ng atmosphere. After pyrolyzed at 1800 degrees C, the derived ceramics were composed of h-ZrB2, ZrC, and free carbon with a formula as ZrB1.38C2.18. 2015 Elsevier B.V. All rights reserved.