Hybrid hydrogel was fabricated by a classic sol-gel method using EDC/NHS as crosslink reagent grafting onto the thermoplastic polyurethane (TPU), nonwoven fabric, for controlled release of drug. In this study, precursor acetic acid (AA) was used to plasma deposit on the surface of TPU to form a hydrophilic thin film. Hybrid hydrogel was investigated through scanning electron microscopy (SEM), water contact angle (WCA) measurement, Fourier transform infra-red (FTIR) spectroscopy, UV/V is spectroscopy, equilibrium swelling ratio, MTT assay and drug delivery system studies. This polyelectrolyte complexes (PECs) formed hydrogel, pH-sensitive type, was evaluated at pH value of 1.2 and 7.4 of buffer solution and at temperature of 37°C to observe its rate of swelling and drug release features with caffeine. Moreover, the mechanism of caffeine release from membrane devices (n=0.58) are anomalous transport, non-Fickian diffusion, the value of n lies between 0.43 and 0.85. It has an excellent release ratio up to about 90% absorption cumulative amounts of caffeine at pH 7.4 after 8h and could be a beneficial carrier for fragile drugs.