The refractive index study of copoly(arylene-siloxane)s constructed with amide, ester, or ether linkage units was conducted to synthesize a step-growth polymer for application in flexible displays. The copoly(arylene-siloxane) based materials have potential use in optical applications due to their durability, flexibility, and possession of good optical clarity properties when compared to conventional silica-filled polydimethylsiloxane-based materials. Measurement of refractive index (RI) was used as the main mode of analysis due to its direct correlation to optical clarity and material flexibility. Synthesis and characterization, including RI compiled data, was performed for six series of step-growth polymers. Effects of different linkage units, namely amides, esters, and ethers, adjacent to at least one six-membered cyclic unit (aromatic or aliphatic) were evaluated. It was observed that the refractive index of these polymers was directly proportional to the aryl content; however, the influence on RI was not equal across all types of linkage units. The highest RI copolymer, poly(4,4-methylenediphenyl diisocyanate-co-carbinol-terminated polydimethylsiloxane) (MDI-SD1.0k), yielded refractive index 1.470 and molecular weight (Mn) 16,100 g/mol; however, the copolymer poly(toluene-2,4-diisocyanate-co-carbinol-terminated polydimethylsiloxane) (TDI-SD) had the highest RI (1.462) per phenyl content. The 4,4-methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate (TDI), and hydrogenated methylenediphenyl-4,4-diisocyanate (HMDI) amide containing linkages best improved the refractive indices of the materials studied.