Nowadays polymer dressings are expected to possess multiply functions. Besides acting as physical barriers, dressings may provide for the injured tissue species able to turn wound healing process faster and painless. In this way, dressings can be designed aiming to enable the release of drugs. The possibility to modulate drug release kinetics is a desired characteristic to be achieved in order to turn drug delivery systems adequate to specific treatments. However, hydrophilic drugs and hydrophobic polymers incompatibility hinders such modulation and a long-term release cannot be achieved efficiently. Here we present the design of poly(lactic acid) (PLA) membranes containing iron-based Layered Double Hydroxide (LDH) particles able to storage a hydrophilic anionic drug (derived from the non-steroidal anti-inflammatory naproxen). LDH particles are excellent candidates to compose multifunctional composites. They may present diverse biocompatible compositions, possess an elevated encapsulation capacity and tends to promote drugs sustained release by its own, besides assisting tissues regeneration process. Nanofibrous membranes were prepared by the combination of electrospun PLA and electrosprayed LDH as alternated layers (approach A) and also by both technics performed at the same time (approach B). In approach A, by varying the thickness of the PLA fibrous layers, it was possible to easily modulate the drug release rate. Half of drug content was released after 1, 4 and 17 days for the membranes containing the thinnest, the intermediate and the thicker PLA layers, respectively, and after 56 h for the membrane prepared by the approach B. Naproxen release was kept for 18 days for the thinnest membrane, 59 days for the membrane prepared by the approach B and 66 days for the thicker membranes. We believe that this work can inspire the development of new functional membranes with tunable drug release profile thanks to the versatile electrospinning and electrospraying techniques.