Crystallization Time (min) PCL block. PCL homopolymer. Crystallization Time (min)

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1 Figure S-1 Crystllinity of PCL Chins PCL homopolymer T c = -54 o C D = 13. nm PCL lock Crystlliztion Time (min) Crystllinity of PCL Chins PCL lock PCL homopolymer T c = -45 o C D = 17.9 nm Crystlliztion Time (min) Figure S-1. Time evolution of crystllinity X C plotted ginst crystlliztion time t for PCL homopolymers (open circles) nd PCL locks (closed circles) oth confined in n identicl nnocylinder with the dimeter D = 13. nm () or 17.9 nm (). 29 The crystlliztion temperture T c is shown in ech pnel.

2 Figure S-2 R-PCL--PS c d PCL Blocks PCL Homopolymers Figure S-2. Schemtic illustrtion showing the strtegy to prepre vrious PCL homopolymers sptilly confined in nnocylinder. The chemicl rection of ONB y light is lso shown.

3 Figure S-3 Normlized Asorption t 254 nm (.u.) PCL--PS PCL--PS PCL--PS PS PS min 1 min 32 min Photoclevge Yield ~ Elution Time (min) Irrdition Time (min) Figure S-3. () GPC chromtogrms of PCL--PS (top) nd smples fter irrdition for 1 min (middle) nd 32 min (ottom) (lck curves). Red, yellow, nd lue curves represent the results of deconvolution using Gussin functions, nd correspond to dimerized PS homopolymers, unrected PCL--PS copolymers, nd PS homopolymers, respectively. () Photoclevge yield plotted ginst irrdition time for PCL--PS with M EG = 43 g/mol. The finl yield is.87, which is similr to ll the PCL--PS copolymers with vrious ulky end-groups.

4 Figure S nm PCL-PS 13.3 ~ 13.9 nm PCLh PCLh/PCL-PS PCLh/PCL/PS 12.9 nm 12.9 nm PCL/PS PCL-PS c 12.6 nm 12.9 nm PSO PCL-PS PCL-PS/PSO PCL/PS/PSO Figure S-4. The strtegy to prepre PCL homopolymers (with MEG = 43 g/mol) confined in nnocylinders with vrious D rnging from 12.6 to 13.9 nm. () A smll mount of PCL homopolymers (PCLh, Mn = 8,5 g/mol, Mw/Mn = 1.6) is dded to slightly increse D. () Originl PCL--PS with D = 12.9 nm. (c) A smll mount of PS oligomers (PSO, Mn = 2,44 g/mol, Mw/Mn = 1.1) is dded to slightly decrese D.

5 Figure S-5 8 Het Flow (Endo. Up) Heting t 1 o C/min Het Flow (Endo. Up) PCL A-PCL C-PCL M-PCL PCL A-PCL C-PCL M-PCL Cooling t -1 o C/min 5 55 Temperture ( o C) 6 6 c PCL A-PCL 25 C-PCL M-PCL 2 PS-PCL 15 Cooling t -1 o C/min Heting t 1 o C/min -PCL A-PCL C-PCL M-PCL PS-PCL Temperture ( o C) 5 d 6 Figure S-5. DSC curves during cooling t -1 o C/min from the melt ( nd ) nd heting t 1 o C/min fter isotherml crystlliztion (c nd d) for ulk PCL homopolymers ( nd c) nd confined PCL homopolymers ( nd d). The exothermic pek during cooling cnnot e oserved for confined PCL homopolymers ().

6 Figure S-6 c d -PCL-PS (morphous) A-PCL-PS (morphous) C-PCL-PS (morphous) M-PCL-PS (morphous) Intensity (.u.) -PCL-PS (crystllized) -PCL/PS (morphous) A-PCL-PS (crystllized) A-PCL/PS (morphous) C-PCL-PS (crystllized) C-PCL/PS (morphous) M-PCL-PS (crystllized) M-PCL/PS (morphous) -PCL/PS (crystllized) A-PCL/PS (crystllized) C-PCL/PS (crystllized) M-PCL/PS (crystllized) s (nm -1 ) s (nm -1 ) s (nm -1 ) s (nm -1 ) Figure S-6. SR-SAXS curves of vrious smples. Blck roken curves: morphous stte efore irrdition (denoted R-PCL-PS, R =, A, C, or M), lck solid curves: crystllized stte efore irrdition, colored roken curves: morphous stte fter irrdition (R-PCL/PS), colored solid curves: crystllized stte fter irrdition. () -PCL-PS nd -PCL/PS, () A-PCL-PS nd A- PCL/PS, (c) C-PCL-PS nd C-PCL/PS, nd (d) M-PCL-PS nd M-PCL/PS. The verticl roken lines represent the primry pek positions. The colored solid curves re summrized in Figure 4 to compre their pek positions.

7 Figure S-7 15 Nnocylinder Dimeter (nm) Moleculr Weight of End-groups (g/mol) 6 Figure S-7. Nnocylinder dimeter D plotted ginst the moleculr weight of endgroups M EG for PCL--PS copolymers with vrious end-groups. The red roken line represents D for the originl PCL--PS with M EG = 43 g/mol (= 12.9 nm).

8 Figure S-8 Melting Temperture ( o C) (nm) 2.45 ( o C) Crystllinity (nm) Nnocylinder Dimeter (nm) 15 Figure S-8. Melting temperture T m () nd crystllinity X C () plotted ginst nnocylinder dimeter D for confined PCL homopolymers with M EG = 43 g/mol (-PCL).

9 Figure S-9-2 In (1/t 1/2 / min -1 ) (nm) Nnocylinder Dimeter (nm) Figure S-9. Inverse of hlf-time of crystlliztion 1/t 1/2 (proportionl to the crystlliztion rte) semi-logrithmiclly plotted ginst nnocylinder dimeter D for confined PCL homopolymers with M EG = 43 g/mol (-PCL, squres) nd with ulky end-groups (circles).