A cross-linked polysiloxane carrying non-ionic amphiphilic side-groups attached with their hydrophobic end to the polymer backbone is synthesized. The amphiphilic groups are selectively deuterated at the alpha-position of the hydrophobic alkyl chains. The phase behavior with water is studied by deuterium nuclear magnetic resonance spectroscopy. A lamellar phase (L(alpha)) is observed on the low-water-concentration side of the liquid-crystalline regime. The domains of the L(alpha)-phase can be aligned macroscopically by uniaxial compression of the sample.