The alignment and cross-linking of chiral liquid crystal (LC) phases has been used to generate ordered noncentrosymmetric polymer networks with a variety of interesting optical and transducer properties. Typically, cross-linkable chiral LC mixtures are prepared by adding nonreactive chiral dopants to achiral LC diacrylate monomers for ease of preparation. Examples of intrinsically chiral LC diacrylates which exhibit chiral smectic phases are rare because of the difficulties associated with the design of such monomers. Herein, we present the stereospecific synthesis and subsequent photopolymerization of achiral smectic : diacrylate 1, which is derived fr om (S)-ethyl lactate. Monomer 1 exhibits an enantiotropic smectic A* phase from 49.2 to 71.0 degrees C upon heating at 0.5 degrees C/min and from 71.2 to 39.3 degrees C upon cooling at the same rate. The smectic A* phase of the chiral monomer can be homeotropically and homogeneously aligned and subsequently photopolymerized to yield highly uniform, noncentrosymmetric polymer films of predefiined symmetry. Upon rapid cooling at 5.0 degrees C/min, the monomer also exhibits a metastable, monotropic ferroelectric smectic C* : phase from approximately 35.5 to 33.0 degrees C. The cross-linking of this metastable phase will also be discussed.