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Controlling morphology of polysiloxane blends crosslinked by the hydrosilylation reaction followed by pyrolysis constitutes a robust strategy to fabricate polymer-derived ceramics (PDCs) for a number of applications, from water purification to hydrogen storage. Herein, we introduce a dissipative particle dynamics (DPD) approach that captures the phase separation in binary and ternary polymer blends undergoing hydrosilylation. Linear polyhydromethylsiloxane (PHMS) chains are chosen as preceramic precursors and linear vinyl-terminated polydimethylsiloxane (v-PDMS) chains constitute the reactive sacrificial component. Hydrosilylation of carbon–carbon unsaturated double bonds results in the formation of carbon–silicon bonds and is widely utilized in the synthesis of organosilicons. We characterize the dynamics of binary PHMS/v-PDMS blends undergoing hydrosilylation and ternary blends in which a fraction of the reactive sacrificial component (v-PDMS) is replaced with the non-reactive sacrificial component (methyl-terminated PDMS (m-PDMS), polyacrylonitrile (PAN), or poly(methyl methacrylate) (PMMA)). Our results clearly demonstrate that the morphology of the sacrificial domains in the nanostructured polymer network formed can be tailored by tunning the composition, chemical nature, and the degree of polymerization of the sacrificial component. We also show that the addition of a non-reactive sacrificial component introduces facile means to control the self-assembly and morphology of these nanostructured materials by varying the fraction, degree of polymerization, or the chemical nature of this component. Full article