The present invention relates to a piezoelectric fiber having excellent flexibility, the piezoelectric fiber employs a conductive fiber member as an inner electrode, on which a piezoelectric polymer layer, an outer electrode and a coating layer are sequentially formed, thereby having excellent flexibility and sufficient elasticity to be sewed, woven, knotted or braided. Therefore, the piezoelectric fiber can be applied in power supplies for a variety of sizes and types of wearable electronic devices, portable devices, clothing, etc. In addition, since the piezoelectric fiber has excellent piezoelectricity and durability because of the above-described structure, it can effectively convert deformation or vibration caused by external physical force into electric energy, and thus can replace existing ceramic-based and polymer piezoelectric bodies, etc. Furthermore, an economical and simple method of manufacturing a piezoelectric fiber having excellent piezoelectricity is provided.