Lithium diisopropylamide (LDA), in the presence of diisopropylamine (DPA), initiates the polymerization of 1,4-, or 1,3-divinylbenzene (DVB) to form a soluble poly(divinylbenzene). Initiation was confirmed to take place by addition of an alkylamino group to the DVB molecule. The population of the triad tacticity of the soluble poly(DVB) suggests the steric course of the polymerization reaction to proceed according to Bernoullian statistics with respect to the diad placements,mandr. The chain-transfer reaction was found to take place through proton transfer from DPA to the growing chain end. A kinetic study of the reaction between lithium alkylamide and poly(DVB) was carried out for comparison with some other styrene derivatives. The second-order rate constant (k) of the reaction between lithium diethylamide and the vinyl group of poly(DVB) was 1.19 × 10−3L·mol−1·s−1, which is only about one-fiftieth of that for 1,4-DVB. LDA was found to metalate the methyl group of 4-methylstyrene to form 4-vinylbenzyllithium without any side reaction. This carbanion has the structure of 10π-conjugation and is stable in the reaction system for more than 30 min. The vinylbenzyl anion is regarded as a model for the growing end of poly(DVB). On the basis of these results, the reason for formation of soluble poly(DVB) in the LDA-induced DVB polymerization is summarized as follows: (i) Relatively short life time of the growing carbanion owing to chain transfer by DPA; (ii) lower reactivity of the pendent vinyl groups of the soluble poly(DVB) compared with those of DVB monomer; and (iii) lowered reactivity of the growing carbanion, which has a stabilized 10π-conjugation.