Facile methods to improve the dissolution rate of poorly water-soluble drugs are highly sought after. In this study, a modified coaxial electrospinning process was exploited to create medicated amorphous nanocomposites, an approach characterized by the application of a Teflon-coated coaxial spinneret. The hydrophilic polymer hydroxypropyl methylcellulose and the active ingredient tamoxifen citrate (TAM) were selected as the drug carrier and model drug, respectively. Their electrospun nanocomposites showed linear morphology with the drug presented in an amorphous state. The loaded cargoes could be released from the nanocomposites simultaneously when they were placed in the dissolution media, showing faster dissolution rates than their counterparts (physical mixtures). Based on the reasonable application of the polymeric carrier, the reported protocols not only provided an approach to enhance the dissolution of poorly water-soluble drugs, but also exhibited a method to facilitate the implementation of coaxial electrospinning.