Film preparation of a novel polymer photonic material, PPESK, was investigated systemically. The influence of solvent hydrophilicity on film quality was analized. A good waveguide film with homogeneous thickness (better than 1%) and identical refractive index (better than 0.03%) was fabricated by nitrogen atmosphere protection. The optical properties of PPESK film, including refractive index, birefringence, thermal-optical coefficient and optical loss, were measured and characterized by prism-coupling technique, and the optical loss was measured to be lower than 0.24 dB/cm at 1310 nm, and lower than 0.52 dB/cm at 1550 nm. The results showed that PPESK was a promising photonic polymer material due to its fine optical performance.