Bisphenol A, (2,2-bis(4-hydroxyphenyl)propane, BPA)-free polycarbonate (PC) from six-membered di-cyclic carbonate, di-trimethylolpropane di-cyclic carbonate (DTMPC) was developed as a new type of PC by ring opening homo-polymerization. The polymerization was controlled by using metal-free organic-based catalyst systems. The results indicated that the conversion rate depends on the basicity of the catalyst in the order of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 4-dimethylaminopyridine (DMAP), triethylamine (TEA) from high to low. Over 99% conversion of DTMPC was obtained at 130°C within 15 min by TBD, DBU and DMAP. The resulting PC as a homo-polymer showed high optical transparency and hardness, low swelling property in organic solvents, and thermally stable at temperatures as high as 200 °C. High cell viability as the cyto-compatibility of C3H 10T1/2 cells seeded directly on the surface of PC films was obtained. This implied that PC is a viable material for biomedical and consumer products applications where safety is an important consideration.