Si–B–C–N ceramics were synthesized from boron modified poly(vinyl)silazanes with the chemical formula (B[C₂H₄–Si(CH₃)NH]₃)_n. The originally amorphous materials are crystallized at temperatures in the order of 1,800–1,900 °C, which results microstructures with grain sizes significantly below 100 nm. Several parameters of the heat treatment, including temperature, holding time and atmosphere, affect the resulting nanostructures. This and the chemical and phase composition were studied via X-ray diffraction (XRD), transmission electron microscopy (TEM), electron spectroscopic imaging (ESI) and spectrochemical analysis in order to gain an understanding of the mechanisms, which control the crystallization behavior. Ceramic samples were also produced using different particle sizes of the precursor polymer in order to quantify the effect of the varying specific surface on the crystallization behavior.