Novel amphiphilic polymer co‐networks (APCNs), poly(N‐acryloyl‐L‐alanine)‐l‐polydimethylsiloxane (denoted as PNAA‐l‐PDMS), are prepared, and exhibit remarkable pH‐responsiveness, chiral‐recognition, and enantioselective‐release abilities. The APCNs are prepared by free‐radical copolymerization starting from N‐acryloyl‐L‐alanine (NAA) and methacrylate‐terminated poly(dimethylsiloxane) (M‐PDMS) as co‐(macro)monomers. The APCNs show pronounced pH‐sensitivity, evidenced by a reversible swelling–deswelling transition upon a cyclicly altering pH. The chiral co‐networks are applied for enantioselective recognition and release. A maximum adsorption is achieved towards D‐proline (61%), whereas for L‐proline, it is only 10%. More interestingly, the release for the L‐proline is 90%, whereas for the D‐proline, only 70% is released.