A novel two-layered pain-relieving wound dressing was prepared from a combination of biocompatible polymers: carboxymethylcellulose and polyethyleneoxide, and two types of pain-relieving drugs: the non-steroid anti-inflammatory diclofenac and the local anesthetic lidocaine. To achieve the two-layered structure, electrospinning and impregnation of a commercially available wound dressing Aquacel(A (R)) were used for preparation of respective layers. The electrospun nanofibers have been shown to possess similar features as found in the extracellular matrix, an important component of the skin. This characteristic could significantly contribute to the efficiency of wound healing. The second layer is based on Aquacel(A (R)), an important wound dressing in modern wound care. Since pain can drastically lower the wound healing process, as well as it is known to decrease the overall quality of patient life, pain-relieving drugs are very interesting for wound care applications. For efficient pain reduction, two types of drugs were used. When combined, these can cover different types of wound-related pain (due to the cause and treatment) and hence additionally aid the wound healing process. The combined features of the incorporated pain-relieving drugs and the mentioned materials are therefore very interesting for future studies toward clinical testing of possible prototype products.