This work deals on the preparation of silicon oxycarbide (SiOC) and silicon boron oxycarbide (SiBOC) ceramics from pyrolysis involving alkoxysilanes with different organic groups. Boron content, organic substituent and annealing time were evaluated on crystallization and composition of resulting ceramics. B-free precursors composed of methyltriethoxysilane (MTES), phenyltriethoxysilane (PTES) and vinyltrimethoxysilane (VTMS) were obtained by the sol-gel method, whilst B-containing precursors were prepared by adding to each alkoxysilane a proper amount of boric acid resulting in B/Si atomic ratios of 0.1 and 0.5. Precursors were pyrolyzed at 1500 °C for 1 and 3 h to produce respective SiOC and SiBOC ceramics. X-ray diffraction (XRD) patterns revealed enhanced SiC phase crystallization for PTES-derived ceramics, followed by those containing vinyl and methyl groups, which was also confirmed by X-ray photoelectron spectroscopy (XPS) from percentages of Si-C and Si-O bonds. Csp2 and Csp3 amounts varied among ceramics, indicating direct influence of organic substituent on conductive carbon phase development. Boron addition induced the growth of SiC crystallites, having more evident effect in matrices with higher proportions of amorphous fraction and lower residual carbon amounts. Organic group nature, boron content and annealing time played an important role for production and evolution of SiC and C phases into ceramics.