This review highlights recent (2000-2004) advances and developments regarding the synthesis of block copolymers with both linear [AB diblocks, ABA and ABC triblocks, ABCD tetrablocks, (AB)n multiblocks etc.] and non-linear structures (star-block, graft, miktoarm star, H-shaped, dendrimer-like and cyclic copolymers). Attention is given only to those synthetic methodologies which lead to well-defined and well-characterized macromolecules.