High refractive index polymers (HRIPs) have drawn increasing attention for their various optoelectronic applications. New HRIPs with excellent transparency, which could be facilely synthesized are highly demanded. Herein, sulfur-containing all organic HRIPs with refractive indices up to 1.8433 at 589 nm and excellent optical transparency even in micrometer scale in the visual and RI region as well as high weight-average molecular weights (up to 44500) were obtained by our newly established organobase catalyzed polymerization of bromoalkynes and dithiophenols in excellent yields (up to 92%). Notably, the fabricated optical transmission waveguides using the resultant HRIP with the highest refractive index displayed a reduced propagation loss compared with that generated by the commercial material of SU-8. In addition, the tetraphenylethylene (TPE) containing polymer also exhibit a reduced propagation loss and could be used to examine the uniformity and continuity of optical waveguides with naked eyes because of its aggregation-induced emission feature. Thus, this work not only provides new kind of all organic HRIPs potentially applicable in optical integrated field, but also develops a facile thiol-yne polymerization toward HRIPs.