We demonstrate a novel method to fabricate arrays of resorcinolformaldehyde xerogel (RFX) based high aspect ratio (HAR) threedimensional (3-D) hierarchical C-MEMS structures. Starting from a master pattern of HAR 3-D posts fabricated in SU-8 negative photoresist by photolithography, a negative PDMS stamp with arrays of holes was prepared by micromolding. The PDMS stamp was then used to fabricate HAR 3-D RFX posts by replica molding. The 3-D RFX posts thus fabricated were electrosprayed with SU-8 or an RF sol in the form of submicron or nano sized droplets and followed by pyrolysis to yield HAR 3-D hierarchical carbon posts. To characterize their use in C-MEMS based batteries, galvanostatic (charge and discharge) experiments on RFX derived carbon showed that it can be reversibly intercalated with Li ions and possesses superior intercalation properties as compared to SU- 8 derived carbon which is a widely used material in C-MEMS. ©Copyright 2014 by The Electrochemical Society.All rights reserved.