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Polyacetylene, a versatile material with an electrical conductivity that can span 7 orders of magnitude, is the prototypical conductive polymer. In this letter, we report the observation of a significant Overhauser effect at the high magnetic field of 14.1 T that operates at 100 K and room temperature in both linear and cyclic polyacetylene. Significant NMR signal enhancements ranging from 24 to 45 are obtained. The increased sensitivity enabled the characterization of the polymer chain defects at natural abundance. The absence of end methyl group carbon-13 signals provides proof of the closed-loop molecular structure of cyclic polyacetylene. The remarkable efficiency of the soliton based Overhauser effect DNP mechanism at high temperature and high field holds promise for applications and extension to other conductive polymer systems.