Complex coacervates can form through the electrostatic complexation of oppositely charged polymers. The material properties of the resulting coacervates can change based on the polymer chemistry and the complex interplay between electrostatic interactions and water structure, controlled by salt. We examined the effect of varying the polymer backbone chemistry using methacryloyl- and acryloyl-based complex coacervates over a range of polymer chain lengths and salt conditions. We simultaneously quantified the coacervate phase behavior and the linear viscoelasticity of the resulting coacervates to understand the interplay between polymer chain length, backbone chemistry, polymer concentration, and salt concentration. Time-salt superposition analysis was used to facilitate a broader characterization and comparison of the stress relaxation behavior between different coacervate samples. Samples with mismatched polymer chain lengths highlighted the ways in which the shortest polymer chain can dominate the resulting coacervate properties. A comparison between coacervates formed from methacryloyl vs acryloyl polymers demonstrated that the presence of a backbone methyl group affects the phase behavior, and thus the rheology in such a way that coacervates formed from methacryloyl polymers have a similar phase behavior to those of acryloyl polymers with similar to 10x longer polymer chains.