SiOxCy thin films were deposited by plasma polymerization. The stress of the deposited SiOxCy thin films can be modified by adjusting the beam current, the anode voltage, and the flow rate of hexamethyldisiloxane (HMDSO) gas and oxygen. Reducing the beam current or increasing the flow rate of HMDSO gas increased the linear/cage structure ratio and turned the stress of the SiOxCy thin films from compressive to tensile. The linear/cage structure ratio can be adjusted by changing the composite parameter, W[FM]c/[FM]m, to control the stress of the deposited plasma polymer films. Multilayers of TiO2/SiO2/TiO2 were coated on a SiOxCy plasma polymer film herein, reducing their stress by 70% from 0.06 to 0.018 GPa. The refractive index is 1.55, and the absorption coefficient is less than 10-4 at 550 nm of the SiOxCy films. Superior optical performances of SiOxCy thin films make their use in optical thin films.