pH-sensitive random P(nBA1–x-stat-AAx)100 (MHx) and block–random P(nBA1–x-stat-AAx)100-b-PAA100 (DHx) amphiphilic copolymers have been synthesized, where x stands for the molar ratios of pH-sensitive hydrophilic acrylic acid (AA) units statistically distributed with hydrophobic n-butyl acrylate (nBA) ones within the random block. Static and dynamic light scattering revealed that self-assembly of the random associating block (MHx) and block–random (DHx) copolymers is strongly affected by the pH and ionic strength of the solution and also by the amount of AA units within the MHx blocks. Below a characteristic pH, MHx self-assembles into finite size spherical particles that grow in size with decreasing pH until they eventually become insoluble. DHx self-assembles into similar spherical particles, but the hydrophilic PAA100 corona surrounding the MHx core prevents insolubility at low pH. Self-assembly of DHx at higher pH is fully correlated to that of the neat MHx blocks, indicating that it is possible to con...