A polymer blend of a partially-branched phenyl-substituted polysilane, (Ph2Si)(0.85)(PhSi)(0.15), and polystyrene (1:1 by weight) has been prepared to produce silicon oxycarbide (Si-O-C) composite materials through pyrolysis in the temperature range 700-1200 degrees C under an argon atmosphere. According to elemental analysis results, carbon is a major constituent in a series of Si-O-C composite materials obtained in this study. Completely amorphous features were observed for the composite materials obtained between 700 and 1100 degrees C, while a clearly discernible crystalline evolution of silicon carbide (SiC) phases was found in a glass network of the composite material obtained at 1200 degrees C. This paper also deals with electrochemical lithiation and delithiation for the series of Si-O-C composite materials. The first delithiation capacities of these composite materials were highly dependent on pyrolysis temperatures. The composite material obtained at 700 degrees C had the maximum delithiation capacity of ca. 800 mA h g(-1), while the composite material obtained at 1200 degrees C showed the minimum delithiation capacity of ca. 330 mA h g(-1). The crystalline evolution of SIC phases is thought to cause such a drastic decrease in delithiation capacity at 1200 degrees C. (C) 2013 Elsevier B.V. All rights reserved.