Although high-boiling non-solvent induced macrophase separation in emulsion droplets has been widely applied for the fabrication of polymeric capsules,p recise control of their structures remains ag reat challenge.H erein, block copolymer capsules with tunable shell structures were fabricated by employing an on-solvent as al iquid template in emulsion droplets.T he properties of the non-solvents dictate the phase separation sequence in the droplets and the capsule formation mechanism. Tw od ifferent pathwaysf or capsule formation were observed, and could be applied to predict the shell structure.T he structured capsules could be transformed into mesoporous capsules,w hichd emonstrated an intriguing structure-dependent release behavior.C apsules with spherical shell structures displayed the best permeability,w hile those with lamellar shell structures showed the slowest release,b ut with astepwise profile.After loading with an anticancer drug, different capsules induced different apoptosis ratios in cancer cell studies.Polymeric capsules are of great importance to many applications,e specially for protecting loaded cargoes against ah arsh environment and releasing them upon exposure to external triggers. [1][2][3][4] Many approaches, [5][6][7] such as phase separation in emulsion droplets, [8][9][10] sacrificial template guided polymerization, [11,12] layer-by-layer assembly techniques, [13][14][15] self-assembly of block copolymers (BCPs) in selective solvents, [16][17][18][19][20] and others,h ave been introduced for preparing polymeric capsules.A mong these methods,t he macrophase separation of ahigh-boiling non-solvent (HBNS, e.g.,l ong-chain alkanes) in emulsion droplets containing al ow-boiling good solvent (LBGS,e .g., chloroform) and ahomopolymer has been developed as asimple yet versatile strategy for obtaining homopolymer capsules. [21][22][23] However, for BCP capsules,the capsule formation process is much more complicated as microphase separation (between blocks) and macrophase separation (between HBNS and BCPs) occur simultaneously in the droplets.C respy and co-workers recently reported the fabrication of BCP patchy capsules using hexadecane (HD) as the liquid cores. [24][25][26] However,the effect of polymer-solvent interactions on the capsule shell structure needs further exploration. Nowadays,i ti ss till agreat challenge to generate BCP capsules with tunable shell structures in ac ontrolled fashion.Although BCP capsules are robust enough for cargo loading and release,t hey are semipermeable and only allow for very small molecules to be loaded and released owing to the hydrophobic shell. To overcome this disadvantage, capsules with stimuli-responsive shells have been designed as smart nanocarriers to encapsulate functional species and release them in response to external triggers. [27][28][29][30] Furthermore,t ot une the release behavior, [20,[31][32][33][34] capsules with stimuli-responsive mesoporous shells are excellent candidates for controlling the release of payloads. [35][36][37][38] Remar...