The synthesis, rheological, and fluorescence properties of a cationic water-soluble copolymer, naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer), poly(DSQADMAPM)/NA, are reported. When fluorescent hydrophobes (naphthyl group) are incorporated into the cationic copolymer, the photophysical response may effectively probe solution behavior on the microscopic level. The salt and pH responsiveness inherent to the cationic copolymer systems is a function of ionic group type. Experimental results indicate that I-E/I-M increases steadily with increases in polymer concentration and I-E/I-M values for a given polymer concentration are higher in salt. At low pH values, I-E/I-M is high and excimer emission increases as the quaternary amino groups (R4N+) are screened out. Dynamic light scattering (QELS) measurements indicate that diffusion coefficients of the cationic copolymer increase and the hydrodynamic diameters decrease with increasing salt concentration. Viscosity studies reveal that the polymer coil shrinks as salt is added. In fluorescence quenching study, the reduction in the quenching efficiency of thallium (Tl+) with salt addition can arise from enhanced compartmentalization of naphthalene labels as added electrolyte enhances intrapolymer micellization. The intrapolymer micelle is easily formed, indicating that the thallium ion has difficulty in reacting with bound naphthalenes located in the shrunk polymer coil. The cationic copolymer is depicted as an expanded polymer coil in deionized water because of intra- and interchain repulsions. Consequently, salt addition breaks down the repulsions and enhances intrapolymer micellization.