Anionic polyelectrolytes can be used for a variety of applications, including flocculation and enhanced oil recovery. While it is widely recognized that polyelectrolyte synthesis is impacted by the pre‐polymer formulation and polymerization conditions, the specific relationships between these factors and the subsequent polymer properties are not well understood. Therefore, the current work intends to improve understanding of ionic strength (IS) effects during the copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) and acrylamide (AAm). The aims of the study were (i) to use in situ H1 NMR to study copolymerization kinetics, and (ii) to determine how increasing IS impacts copolymerization kinetics (and, by extension copolymer microstructure). It was found that altering IS prior to copolymerization had significant impacts on the reactivity ratios, and therefore impacted the microstructure through multiple mechanisms. Increasing IS caused a crowding effect, where the propagating chain developed a random coil conformation and caused steric hindrance of the large AMPS monomer, decreasing the likelihood of AMPS propagation. When the IS was increased further, the ionic shielding effect was more impactful, increasing the likelihood of AMPS propagation. Ultimately, this work will make it possible to manipulate IS to synthesize AMPS/AAm copolymers with specific desirable properties for target applications.This article is protected by copyright. All rights reserved