The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (Ia /Ib) of DMABA in the aqueous $alpha-CD$ solutions are greatly decreased while the Ia /Ib values in the aqueous B-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in $alpha-CD$ or B-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of νs (CO2-)(1380 cm-1 ) with appearance of ν(C-OH)(1280 cm -1) band, respectively. Thus, in the aqueous B-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen-bonded with the secondary hydroxyl group of B-CD while in aqueous and $alpha-CD$ solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous B-CD solutions the enhancement of the Ia /Ia value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of B-CD as well as the lower polarity of the rim of the B-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/ B-CD complex in the presence of silver colloids.