High‐refractive‐index (high‐n) polymers (HRIPs) with a high optical transparency are highly needed in advanced optoelectronic devices. In this work, we report the synthesis and characterization of a series of high‐n, transparent, totally colorless, and high‐sulfur‐containing poly(phenylene sulfide)s (PPSs) bearing a triazine unit. Two new triazine monomers T1 and T2 with hydroxyl and tert‐butyl acetate side chains, respectively, were designed and synthesized to develop PPSs with high‐n and high alkaline solubility. These PPSs were prepared by the single‐phase polycondensation from T1/T2 and commercial aromatic dithiols such as 4,4′‐thiobisbenzenethiol (TBT) and benzene‐1,3‐dithiol (BDT), achieving very high‐n up to 1.7530 at 633 nm, a high optical transparency (T% > 90% @400 nm) and low birefringence (Δn = 0.0014–0.0080), and exhibiting high potential on the application of high‐n photoresists. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 724–731