Subtle structural changes in monomeric building blocks can have an immense effect, whether positive or detrimental, on the resulting properties of conjugated polymers. With this in mind, it is paramount to understand structure-property relationships that serve as the guiding principles for manipulating optical and electrochemical characteristics. Herein, a family of dialkylthiophene-co-propylenedioxythiophene copolymers are synthesized via direct arylation polymerizations, with a key design motif being minimal changes in the structural composition of the propylenedioxythiophene comonomer. Variation in the substitution pattern on the propylene bridge provides insights into the role of stereo- and compositional isomers on the resulting polymer properties. Specifically, time-dependent density functional theory calculations reveal changes in the number and placement of comonomers with varying composition and stereocenters, impacting the calculated absorbance spectra, as evident from calculated absorbance maxima spanning 75 nm, which ultimately manifests in differences in the calculated color. Experimentally, UV-vis absorbance spectroscopy and colorimetry reveal a dependence on the stereo- and regiospecificity, while electrochromic properties, such as contrast and switching times, are not drastically affected by the substitution patterns. Independent of position and functionality, each polymer exhibited a transmittance change greater than 65% at the maximum absorbance wavelength while maintaining the ability to rapidly switch between colored and transmissive states in organic electrolytes. This work highlights how subtle structural changes can manipulate and optimize optical features without sacrificing electrochromic properties such as kinetic switching time and optical contrast. In addition to fundamental insights into monomeric design of propylenedioxythiophene building blocks and their optical and redox characteristics, the results provide an additional structural handle for fine-tuning the observed color of electrochromic polymers.