2-Naphthol (NOH) in its ground state forms a 1:1 complex with β-cyclodextrin (β-CD) both in the absence and presence of linear alcohols. Association constants, Kapp, were measured using a steady-state fluorescence method. Kapp decreases linearly with an increasing number of carbon atoms in the chain of the alcohol, nC, up to nC = 5. We attribute this to a competition between NOH and alcohol for the β-CD cavity. Fluorescence studies confirm the redistribution of NOH from the CD environment to the aqueous phase when alcohols are present. NOH fluorescence is quenched by iodide in all the systems studied. At 2 mM β-CD, alcohols increase the Stern−Volmer constant above the value found in the absence of alcohols. These results suggest that alcohols occupy space within the β-CD cavity with the result that the aqueous NOH concentration is increased. This was further investigated by dynamic fluorescence measurements on the system β-CD:NOH:pentanol. Global biexponential analysis of fluorescence decay data shows tha...