In this contribution,we reported a novel synthesis of block copolymer networks composed of poly(ε-caprolactone) (PCL) and polyethylene (PE) via the co-hydrolysis and condensation of α,ω-ditriethoxylsilane-terminated PCL and PE telechelics.First,α,ω-dihydroxyl-terminated PCL and PE telechelics were synthesized via the ring-opening polymerization of ε-caprolactone and the ring-opening metathesis polymerization of cyclooctene followed by hydrogenation of polycyclooctene.Both α,ω-ditriethoxylsilane-terminated PCL and PE telechelics were obtained via in situ reaction of α,ω-dihydroxyl-terminated PCL and PE telechelics with 3-isocyanatopropyltriethoxysilane.The formation of networks was evidenced by the solubility and rheological tests.It was found that the block copolymer networks were microphase-separated.The PCL and PE blocks still preserved the crystallinity.Owing to the formation of crosslinked networks,the materials displayed shape memory properties.More importantly,the combination of PCL with PE resulted that the block copolymer networks had the triple shape memory properties,which can be triggered with the melting and crystallization of PCL and PE blocks.The results reported in this work demonstrated that triple shape memory polymers could be prepared via the formation of block copolymer networks.