Comblike block copolymers having a poly(chloroethyl vinyl ether) backbone and poly(styrene-b-isoprene) side chains, i.e., PCEVE-g-(PS-b-PI), of different molar masses and chemical compositions were synthesized by "grafting onto" technique using the coupling reaction of acetal-PSLi (F-PSLi) chains onto the reactive functions of a PCEVE backbone, followed, in a second step, by the grafting of living PIDLi chains onto the acetal ends of PS branches activated by trimethyl silyl iodide. The comblike copolymers exhibit low polydispersity, high molar masses, and a controlled number of branches. Their characteristics and behavior were further studied in the solid as thin films and in good and selective solvents. Atomic force microscopy (AFM) shows isolated uniform molecules that adopt an ovoid conformation. The solution behavior of these comblike polymers was investigated by dynamic light scattering (DLS), both in a good solvent of the PS and the PI blocks and in selective solvents of the outer PI blocks. Depending on the solvent quality and the temperature, the comblike copolymers, which remain in the form of isolated molecules, adopt different chain conformations and dimensions, as shown by the drastic variation of the radius of gyration. In a series of hydrocarbon solvents of decreasing quality for the inner PS block, the significant volume decrease of the macromolecule is attributed to the internal shrinkage of the PS blocks. In cyclohexane, a theta solvent for the inner PS block, a strong variation of the comblike size (90% volume change) takes place with the temperature change, directly correlated with the internal expansion/contraction of the inner PS blocks.