本論文研究刮膜製程下，超分子團鏈共聚物薄膜之自組織行為。經由穿透式顯微鏡和掠角小角度Ｘ光散射量測下，我們發現超分子團鏈共聚物薄膜在熱回火過程，內部結構由橢球狀結構，經由rhombohedral之過渡態再轉變成垂直六方排列柱狀結構。利用超分子團鏈共聚物所形成之水平和垂直奈米柱狀陣列模板，透過模板合成方式製備出二氧化鈦孔洞陣列薄膜。最後將製備完成之二氧化鈦薄膜應用於染料敏化太陽能電池工作電極，比較二氧化鈦奈米結構為粒子、水平孔洞陣列、垂直孔洞陣列時的電池效率值。此外，我們也製備出雙層結構工作電極，觀察是否在不同結構的搭配下，效率值之變化。;In this study, we have demonstrated that supramolecular dendron-jacketed block copolymers can be used as nano-sized templates to synthesize high densities of arrays of TiO2 nanostructures Upon tailoring the grafted fractions of small molecules to change the volume fraction of PS segments within self-assembled PS-P4VP(3C12)0.7 films, the nanostructures of the films can be systematically controlled. Preferential incorporation of 3C12 into the P4VP domains changed the volume fraction (f) of the PS domain. When the volume fraction of PS reached f = 0.29 %, the internal nanostructures of the films changed from spherical nanodomains (S) to perpendicularly-oriented nanocylinders (C┴) after being thermally-annealed at 150 oC for 24 h. By analyzing the cross-section images of TEM and scattering patterns of GISAXS, we discovered that the morphological transition of S→C┴ underwent a rhombohedral state. Next we immersed the self-assembled PS-P4VP(3C12)0.7 films in ethanol containing TiF4, by which TiF4 dissolved to form titanium ions in ethanol. Since 3C12 small molecules were soluble in ethanol and have stronger affinity to the P4VP domain than 3C12, the titanium ions could replace 3C12 to preferentially bond the P4VP domains. We also used GISAXS to characterize the structural evolution of the films in an immersion process. Finally the nanodomains were further used as templates to direct the synthesis of nanoporous TiO2 thin films after immersion in solutions containing TiF4 followed by high-intense light exposure. The synthesized TiO2 nanostructures can be further facilely used for electrodes of dye-sensitized solar cells (DSSC). Various nanostructured DSSCs devices were fabricated, and their performances were also tested and discussed in this thesis.