Microsperes (MSs) of porous silica gel modified by aminopropyl groups (APs) on which negatively charged polymer cyclodextrins (PCDs) were sorbed (copolymers of carboxymethyl-β-CD (KMCD) or sulfo-β-CD (SCD) with epichlorohydrin) are used for the detection of vapors of benzene (B), toluene (T), and naphthalene (N). For comparison, MSs with β-CD covalently bound through an AP linker and CD-free AP-MS are used. The N-PCD complexes have binding constants Kb higher by more than an order of magnitude than those of the β-CD monomers and higher fluorescence quantum yields. A method for determining the concentrations of adsorbed PCD is developed. Adsorption isotherms for both PCDs are almost linear in the PCD concentration range of 0–30 mM. The amount of KMCD polymer corresponds to a monolayer surface coverage of MSs at the initial concentration of 30 mM as opposed to the much lower surface density of covalently bound β-CD (0.2/nm2). The fluorescence spectra of hydrocarbons sorbed on MSs from saturated vapors differ substantially from those in aqueous solutions representing broad bands shifted to high wavelengths λ due to the formation of excimers. Fractions of excimers and shapes of their spectra are determined by the subtraction of monomer spectra from the overall spectra of hydrocarbons on MSs. For N on MSs with polymer CD and MSs with covalently bound β-CD, excimers of different types are observed. The kinetics of spectral changes is studied for the inflow of N vapors in the range of 25–1000 s.