For weak polyelectrolytes, the interplay between pH, solvent properties, and polymer structure affects the amount of charges, their distribution, and hence their conformations via Coloumb repulsion. Attractive interactions can also develop between charged and neutral sites counteracting the expected Coulomb-induced expansion. To gauge how such competition affects polyelectrolyte structure and ionization, the titration of a single polyelectrolyte chain, isolated or close to a charged sphere, mimicked with a novel many-body potential model is simulated with Monte Carlo. Apart from showing a 10-fold higher ionization than isolated monomers at low pH, interacting species contracted forming short-range clusters of charged and neutral ionizable groups. The presence of a charged sphere synergically boosted both effects due to monomer interactions, forcing the chains to condense onto its surface at much lower pH. Structural properties, however, seem to be controlled only by the ionization degree despite the presence of the topological restraint represented by the spherical surface. Using Monte Carlo titration results, the equilibrium ionization of isolated chains is also estimated; the results evidence that even weak interactions can easily lead to a doubling of the total charge. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 650-663