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Pain is one of the most common patient complaints encountered by health professionals and remains the number one cause of absenteeism and disability. In the current study, analgesic-eluting bioresorbable porous structures prepared using the freeze-drying of inverted emulsions technique were developed and studied. These drug-eluting structures can be used for coating fibers or implants, or for creating standalone films. They are ideal for forming biomedically important structures that can be used for various applications, such as wound dressings that provide controlled release of analgesics to the wound site in addition to their wound dressing role. Our investigation focused on the effects of the inverted emulsion's parameters on the shell microstructure and on the resulting drug-release profile of ibuprofen and bupivacaine. The release profiles of ibuprofen formulations exhibited a diffusion-controlled pattern, ranging from several days to 21 days, whereas bupivacaine formulations exhibited an initial burst release followed by a three-phase release pattern over a period of several weeks. Higher organic to aqueous phase ratios and higher polymer contents reduced the burst release of both drugs and prolonged their release due to lower porosity. Overall, the drug-eluting porous structures loaded with either ibuprofen or bupivacaine demonstrated a promising potential for use in various applications that require pain relief.