Two flexible and colorless polymers are synthesized based on a phosphorus-containing derivative of a bio-based aromatic aldehyde (4-hydroxybenzaldehyde) by a thiol-ene reaction. Thanks to the high polarizability of phosphorus and sulfur atoms, two polymers display refractive index (n) values of 1.721 and 1.698 at 546 nm, respectively. These data are much higher than those of polyphosphonates (below 1.65) and are comparable to those of polyphosphazenes with undesirable halogens (1.664-1.755). Moreover, both the polymers (TVP-TH1 and TVP-TH2) exhibit a transmittance of above 88% in the wavelength range from 550 to 2000 nm and a transmittance of about 0% in the UV region, indicating their potential application as transparent coatings for hindering the ultraviolet ray and infrared transmitting materials. In particular, these phosphorous-sulfide polymers display good thermostability with a glass transition temperature (T-g) of above 130 degrees C and 5% weight loss temperature (T-5d) of over 310 degrees C. These results imply that new phosphorous-sulfide polymers are very suitable as encapsulation resins for light-emitting diodes (LEDs) and optical materials and as antireflective coatings and microlenses for the image sensors of complementary metal oxide semiconductors (CMOSs).