Significant research efforts have focused on the development of effective means for the detection of organic molecules. These efforts can be divided, very crudely, into those focusing on either electrical-or optical-sensing mechanisms. To date, sensors based on optical measurements have generally proven to be faster, safer, and easier to implement than those employing electrical measurements.[1] In particular, porous materials are well suited for use as templates for optical sensing. Porous silicon is an especially appealing material for these applications due largely to the fact that it can be readily structured using electrochemical etching and/or photolithography. For example, highly reflective porous silicon microcavities can be generated by using controlled etching, resulting in layers of alternating porosities. [2,3] Recently, excellent progress has been made in creating porous silicon films, [4,5] microcavities, [6,7] and arrays of microstructures [8] useful for optical sensing. Generally, these devices rely on the changes in the optical resonance that occur when the porous structure is occupied by the analyte species, allowing for simple and effective detection schemes. However, the versatility of porous silicon is tempered by its instability. As an alternative, porous polymer nanostructures produced from an oxidized porous silicon template have been demonstrated as a way for sensing applications.[9] Micropatterned polymeric gratings have also been demonstrated as a relevant sensing material for detecting organic solvents. For example, instead of using a porous layer-by-layer geometry of a reflection grating, a micropatterning transmission grating (array design) was shown to have the ability to identify a mixture of chemical analytes. [10] In the work reported in this communication, we demonstrate a simple method for optical detection of different organic-solvent vapors based on the holographic fabrication of high-porosity polymer Bragg reflection gratings. Furthermore, these results demonstrate that this photopolymer fabrication technique could potentially be used to create structures suitable for biological applications in aqueous environments. The typical method used to produce periodic porous silicon structures is relatively complicated, requiring a controlled electrochemical etching process in a hydrofluoric acid solution. [1±3,5±9] In contrast, it has recently been demonstrated that organic polymeric materials can yield high-efficiency reflection gratings through a fast and inexpensive holographic photopolymerization technique. [11] In this technique, a prepolymer syrup containing a monomer, a photoinitiator, a co-initiator, and a liquid crystal (LC) is sandwiched between two pieces of glass, and a periodic structure is then formed by applying an optical interference pattern generated using a simple one-beam setup. [12] We have recently demonstrated that porous acrylate polymer grating structures can be created in a similar manner by simply adding a non-reactive solvent, such as acetone or toluene,...