The reaction rate for the end-cross-linking process of vinyl-terminated poly(dimethylsiloxane) by a cross-linker with four Si H liquid-state functionalities in NMR in dependence of the reaction temperature. The properties of the the presence of solvent was studied by H-1 resulting polymer networks, i.e., the gel-point and the formation of the elastically effective network, were monitored in situ during the reaction by single-evolution-time H-1 double-quantum (SET-DQ) low-field NMR It was found that the cross-linking kinetics shows no uniform reaction order for the conversions of the functional groups before the topological gelation threshold of the polymer network. The two NMR methods are combined to investigate the formation of the elastically effective network in dependence of the conversion of the functional groups of the precursor polymers and the crosslinker. The high chemical and time resolution of the experiments enabled an in-depth analysis of the reaction kinetics, allowing us to conclude on a multistage model for PDMS network formation by hydrosilylation-based end-linking in the presence of solvent. We found that the nonuniform network formation kinetics originates from a dependence of the apparent reaction rate on the number of the Si-H groups of the cross-linker that have already reacted during the progress of the reaction. The fastest overall reaction rate is observed in a range until each cross-linker has reacted once on average, and a uniform apparent overall reaction order of unity with respect to cross-linker concentration is only found at a later stage, when multiply reacted cross-linker molecules with similar reactivity dominate.