Pharmaceutical wastewater pollution has reached an alarming stage, as many studies have reported. Membrane separation has shown great performance in wastewater treatment, but there are some drawbacks and undesired byproducts of this process. Selective membranes could be used for pollutant investigation sensors or even for pollutant recovery. The polydimethylsiloxane (PDMS) membrane was first tested on separated and mixed antibiotic (ATB) water solutions containing sulfamethoxazole (SM), trimethoprim (TMP), and tetracycline (TET). Then, the bare and ultra-violet grafted (UV-grafted) PDMS membranes (MMA-DMAEMA 10, GMA-DMAEMA 5, and GMA-DMAEMA 10) were tested in tramadol (TRA) separation, where the diffusion coefficient was evaluated. Finally, the membranes were tested in pertraction with a mixture of SM, TMP, TET, and TRA. The membranes were characterized using the following methods: contact angle measurement, FTIR, SEM/EDX, and surface and pore analysis. The main findings were that TET was co-eluted during mixed ATB pertraction, and GMA-DMAEMA 5 was found to selectively permeate TRA over the present ATBs.