The photophysical properties of two polyazomethine polyrotaxanes (4•αCD and 4•TMS-αCD) composed of pyrene and triazole encapsulated into native and permodified α-cyclodextrin (αCD and TMS-αCD) cavities have been investigated and compared with those of the non-rotaxane 4 counterparts. Rotaxane formation results in improvements of the solubility in organic solvents, as well as better film forming ability combined with a high transparency. The polyrotaxane 4•TMS-αCD was soluble in toluene/DMF1/1 v/v mixture and displayed useful levels of thermal stability. The fluorescence spectroscopy of 4•αCD and 4•TMS-αCD shows an obvious blue shift both in excitation and emission spectra with respect to those of non-rotaxane counterparts. 4•TMS-αCD displays a continuous absorption spectrum, whereas the reference 4 does not show any absorption maximum, neither for its emission maximum, presumably because of its very low solubility in DMF. The improved fluorescence efficiency (ΦPL) of both polyrotaxanes is attributed to the hydrophobic micro-environment within αCD and TMS-αCD cavities. The surfaces of non-rotaxane 4 counterparts showed globular formations with an agglomeration tendency, while the encapsulated 4•αCD and 4•TMS-αCD rotaxane compounds exhibited smoother surfaces, comprised by smaller grains uniformly distributed on the surface of the solid films. The presence of the αCD and TMS-αCD in 4·αCD and 4•TMS-αCD polyrotaxanes affects the LUMO energy levels to a greater extent than its HOMO energy with respect to reference 4. The wetting properties of spin-coated film of 4•TMS-αCD in water (polar) and diiodomethane (apolar), indicates that TMS-αCD makes its surface more hydrophobic. The dispersive and polar components are lower than that of the reference compounds. The doping of the rotaxane structures with iodine (I2) indicated smaller improvements of electrical conductivity (σ) values, which presents a tradeoff with their better solubility, process ability, surface characteristics and ΦPL.