Electron spin resonance (ESR) dating is closely related to thermoluminescence (TL) dating. The principle and procedures of ESR are described together with the application to archaeological materials excavated at Petralona cave in Greece. Atomic models of defects responsible for TL and ESR in calcite are discussed. The age is deduced from the archaeological dose, the total dose of the natural radiation determined by ESR signal intensities, and from the dose rate. The ages by ESR dating are compared with those by TL and ₁₄C dating and also by U-Th dating. The applications to geological and anthropological materials are described with main emphasis on cave deposits.