We have synthesized a new second-order NLO compound containing both the highly active tricyanovinyl electron acceptor group and appropriate funtionality for covalent bonding to an inorganic silica matrix by sol-gel processing. Sub-Micron films of this material can be prepared by spin-coating, and thicker films can be prepared by casting or by spinning multiple layers. After curing at 150 °C, these films exhibit good chemical durability. The chromophores can be aligned by either corona or parallel-plate poling during the curing process. In this paper we will discuss the synthesis of the NLO compounds; sol-gel processing and thin-film preparation; optical, thermal, and chemical properties of the films; and the results of both corona and parallel-plate poling experiments.