In this research, a novel high permittivity ceramic silicone composite substrate (HPCSCS) based antenna design is proposed for RF energy harvesting (RFEH). The HPCSCS is prepared using high-permittivity barium titanate (BaTiO3) ceramic powder mixed with RTV silicone sealant (RTVSS) which possesses a high permittivity value of 11.9. Five different antenna designs were simulated in CST software and one design has been finalized based on design geometry, bandwidth, gain, and reflection coefficient. Moreover, the proposed antenna design is optimized with the addition of a coplanar waveguide. The designed antenna has a thickness of 0.06 mm and provides a wide operating band range from 0.7 GHz to 3 GHz. It provides a reflection coefficient of –32 dB and a positive gain of 1.84 dB at the operating frequency of 2.66 GHz demonstrating the excellent wide bandwidth of 885 MHz. A prototype of the antenna is fabricated and mounted on an HPCSCS for measurement through a vector network analyzer with a good match between the simulated and measured results. The rectenna system (antenna + rectifier) for RFEH has been developed and tested, which achieved a maximum rectifier conversion efficiency of 57 % at 0 dBm and produced a maximum output voltage of 1.35 V at 0 dBm.