We propose a strategy of combination of tailored synthesis and direct analysis of decrosslinked components of the network, which is applicable to quantitative characterization of polymer network. The well-defined polymer networks with cleavable branch units were synthesized by endlinking of 3-armed prepolymer. Via decrosslinking, cleavage at the branch units, the polymer network can be transformed to linear chains, which can be analyzed by normal methods. The length between the branch units, the distribution of the branch units and the fraction of the dangling chains of the network together with the extent of reaction are directly analyzed, which give detailed description of the polymer network. (C) 2016 Elsevier Ltd. All rights reserved.