Main observation and conclusionrnThe on-demand building copoiymer structures,from sequence to architecture,is crucial in understanding the relation between pol-ymer structure and property,meanwhile motivating the innovation of polymer hierarchy.However,the challenge is conspicuous for complicated polymer structures from inherently intricate polymerization.In this work,copolymers with tailored grafting density and distributions were achieved using successive latent monomer and grafting-from strategies.The hydroxyl group functionalized fu-ran/maleimide adduct (FMOH) was selected as the latent monomer for RAFT polymerization of an array of copolymers with tailored localization of hydroxyl group along the main chain.The hydroxyl group further initiated the ring opening polymerization (ROP) of L-lactide or ε-caprolactone,resulting in a library of multicomponent copolymers via grafting-from strategy.The initiating efficiency reached to ～100％ with variable molecular weight (21300-58600 Da) and narrow distributions (DM ＜ 1.25),indicating that such graft copolymers possessed controlled density and distribution of side chains as its linear template.The investigation on thermal properties of the well-defined graft copolymers implied that the precise tailoring over copolymer structures at the molecule level could lead to tunable chemical/physical properties.This work bridged polymer from sequence to architecture,unveiled a new meth-od in creating graft copolymers with programmable structures and provided the insight into the structure/property relationship.