The adsorption of quaternized poly(vinylpyridine) (QPVP) on controlled pore glass (CPG) size, over the ionic strength range 0.001 -0.5 M was found to display nonmonotonic behavior as a function of pore size. Both adsorption kinetics and ionic strength effects deviated dramatically from behavior typical of adsorption on flat surfaces when the ratio of the pore radius Rp to the polymer hydrodynamic radius Rh became smaller than ca. 2. Ionic strength enhancement of adsorption for small pore sizes was observed at much higher salt concentrations than is typical for polycation adsorption on flat surfaces. The amount of polymer adsorbed per unit surface area of glass ΓA, in 0.5 M NaCl, exhibited a shallow maximum at R p/Rh, ≈ 5. Since the value of ΓA for small pore size CPG is strongly depressed by the large surface area, an alternative and more interesting observation is that the amount of polymer adsorbed per gram of CPG, Γw, displays a strong maximum when Rp is equal to or slightly smaller than Rh. The efficiency with which QPVP binds anionic micelles to (negatively charged) CPG (grams of surfactant/grams of QPVP) increases strongly with diminishing pore size, indicating that the configuration of polycation bound to small pores favors micelle binding. Since the micelles are larger than small pores, the results indicate that when Rp < Rh, adsorbed polycation molecules reside only partially within the pore. The results of this study are supported by simulations of polyelectrolytes within cylindrical cavities.