Processable organic materials with large, ultrafast thirdorder susceptibilities, x (3) , could enable all-optical signal processing (AOSP) applications through either fabrication of large-area thick films or integration into hybrid organic/ silicon photonic devices. [1][2][3][4] Conjugated polymers, such as polyacetylene, have been shown to exhibit large optical nonlinearities upon application of intense electromagnetic fields.[3] Despite these nonlinearities, many conjugated polymers are inadequate for photonic applications because they lack sufficient processability, or form films with significant crystallinity [5] or inhomogeneous morphologies [6] resulting in poor optical quality. For example, although films of unsubstituted polyacetylene have been found to possess large third-order susceptibilities, [7][8][9] they also exhibit extensive crystallinity, [10] resulting in poor optical quality and large scattering losses.[11] A more processable soluble diester polyacetylene derivative has been reported; [2] however, only thin films have been produced from this material and the bulky side groups can be anticipated to lead to a reduced nonlinear response through a dilution effect. The diester polyacetylene was successfully used in an image-correlation application performed using degenerate four-wave mixing (DFWM) in the visible region with resonant excitation, although the diffraction efficiency was relatively low, due mainly to the limited interaction length. Ring-opening metathesis polymerization (ROMP) provides for the facile synthesis of a great variety of unsaturated polymers.[12] The ROMP method (Scheme 1) utilizes an organometallic alkylidene-based initiator (e.g., rutheniumbased Grubbs initiators [13][14][15] or four-coordinate tungsten-and molybdenum-based Schrock initiators [16][17][18] ) to polymerize strained-ring olefin monomers. [6,19] The ROMP process allows for in situ polymerization of liquid-phase monomers, which allows facile processing of neat films [11] as well as potential integration of the resulting polymers into micro-or nanostructured photonic devices. Moreover, this method is amenable to independent optimization of monomers and initiators to improve processing conditions, optical quality of films, and the third-order susceptibility of the resulting conjugated polymers.Here we report on the synthesis, processing, and linear and nonlinear optical characterization of substituted polyacetylenes obtained using ROMP of mono-substituted cyclooctatetraene (R-COT) monomers. Polymerization and processing conditions have been developed that have led to thick (2-200 mm), large-area (>1 cm  1 cm) films possessing large third-order nonlinearities in the near-infrared (NIR) region including the telecommunications bands. The good optical quality of a 200 mm thick poly(n-butyl-COT) film allowed for DFWM image correlation under off-resonant excitation to be performed with improved diffraction efficiency relative to that obtained using the diester polyacetylene derivative mentioned above; the resulting di...