Cross-linked polymers prepared by the in-situ polymerization of liquid-crystalline salts were found to work as solid-state hosts with a flexible framework. As a component of such hosts, four kinds of polymerizable amphiphilic carboxylic acids bearing alkyl chains with acryloyloxy (A), dienyl (D), and/or nonreactive (N) chain ends (monomeric carboxylic acids; MAAA, MANA, MDDD, and MDND) were used. The carboxylic acids were mixed with an equimolar amount of a template unit, (1R,2S)-norephedrine (guest amine; GRS), to form the corresponding salts. Every salt exhibited a rectangular columnar LC phase at room temperature, which was successfully polymerized by 60Co γ-ray-induced polymerization without serious structural disordering to afford the salt of cross-linked carboxylic acid (polymeric carboxylic acid; PAAA, PANA, PDDD, and PDND) with GRS. Owing to the noncovalency of the interactions between the polymer framework P and the template GRS, the cross-linked polymers could reversibly release and capture a meaningful amount of GRS. In response to the desorption and adsorption of GRS, the cross-linked polymers dramatically switched their nanoscale structural order. A systematic comparison of the polymers revealed that the choice of polymerizable groups has a significant influence on the properties of the resultant polymer frameworks as solid-state hosts. Among these polymers, PDDD was found to be an excellent solid-state host, in terms of guest-releasing/capturing ability, guest-recognition ability, durability to repetitive usage, and unique structural switching mode.