Model silicone networks obtained by curing linear poly(dimethylsiloxane) (PDMS) chains with end-vinyl groups, (B-2), with a polyfunctional silane-terminated crosslinker of functionality f, (A(f)), through a hydrosilylation reaction have been widely used. In these networks, the principal characteristics of their ultimate molecular structure are strongly affected by the final extent of reaction reached during the crosslinking reaction. This work analyzes the effect of the initial concentration of the reactive end groups on the maximum attainable extent of reaction under normal bulk crosslinking conditions. This was accomplished by examining the reaction between linear B, PDMS chains with difunctional and trifunctional silanes. The experimental results were fitted by an exponential equation to have an empirical equation able to predict the maximum extent of reaction to be obtained as a function of the initial concentration of reactive groups. Molecular parameters relevant to this study, such as the degree of polymerization, the weight-average molecular weight for the A(2) + B-2 system, or the weight fraction of solubles for the A(3) + B-2 system, were calculated with a mean field theory (recursive approach). (C) 2003 Wiley Periodicals, Inc.