Publisher Summary This chapter discusses the excited state properties of higher-order cyclodextrin complexes. In general, the photochemical property of guest, dissolved in homogenous aqueous solution, is affected by the inclusion in the CD cavity. The chapter focuses on high-order CD complexes, whose photophysical and/or photochemical properties have been mechanistically rationalized in the light of available structural information. It presents how stoichiometry and the structural features of the higher order complexes control the excited behavior of the guest molecule. The chapter demonstrates how when more than one guest molecule is involved in the complex, excimer emission can originate owing to the strong guest–guest interactions in the restricted environment. The results obtained from experimental data are shown in the chapter.