An electrostatic discharge (ESD) protection structure for a 3D IC is provided. The ESD protection structure includes a first active layer, a through-silicon via (TSV) device and a second active layer. The TSV is disposed in the first active layer, and the second active layer is stacked with the first active layer. The second active layer includes a substrate and an ESD protection device, wherein the ESD protection device having a doping area embedded in the substrate, and the ESD protection device electrically connects the TSV device.