Wound healing is a complex and dynamic process consisting of devitalized and missing cellular structure replacements and regeneration of tissue layers. Each wound requires individual diagnosis and care in order to remove the barriers for the healing process. It is of relevance that wound dressings are not only to protect from microbial contamination, physical protection and moisture retention, but also to support the normal wound healing and provide important biological molecules and/or active substances for the wound. There is a growing interest in the development of electrospun biocomposite fibers as wound dressings due to their tunable and multifunctional properties. The main advantages of electrospun biocomposite fibers in wound healing process include their resemblance to natural extracellular matrix, high surface-area-to-volume ratio, tunable porosity, sufficient gas exchange and possibility to include different active substances and living cells into the fibers. Electrospinning technology enables to produce ultrafine fibers from different materials by using various setups. Both solution (blend, coaxial and emulsion) electrospinning and green solvent-free electrospinning approaches can be used for producing biocompatible fibers for wound care. Materials suitable for wound dressings are expected to meet the requirements of the wound and to be biocompatible. Multifunctional biocomposite fiber dressings enable to combine the physical and biochemical properties of natural and synthetic polymers together with active substances that are beneficial for wound healing. Furthermore, biocomposite fibers are able to interact with the wound, and their properties can be modified according to the need. This chapter reviews electrospun biocomposite fibers as novel materials for the preparation of wound dressings. The relevant methods and materials for the preparation, and the properties and methods for the analysis of electrospun fibers will be discussed in more detail by considering their suitability for wound care. Data sources will include mainly peer-reviewed literature, reports, patents, and guidelines where available.