In this paper, we report reversible fixation and release of alcohols by a polystyrene derivative bearing acyclic vicinal tricarbonyl moieties (1) and its application to synthesis and reversible cross-linking-de-cross-linking system of a networked polymer. First the reversible fixation and release behavior of alcohols by an acyclic vicinal tricarbonyl compound, 1,3-diphenylpropanetrione (DPPT) as a model compound of 1 was investigated. On the basis of the results, the fixation of n-hexanol to 1 was carried out to provide the n-hexanol adduct of 1 (1-HexOH), which has a hemiacetal structure. On the other hand, heating 1-HexOH in vacua enabled successful recovery of 1 to demonstrate the reversible nature of this system. Furthermore, the reaction of 1 with 1,6-hexanediol proceeded smoothly to give networked polymer, which could be de-cross-linked by heating at 50 degrees C in DMSO/H2O mixture. This result indicates that a novel reversible cross-linking de-cross-linking system of networked polymer was constructed.