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Replacing traditional liquid electrolytes by polymers will significantly improve electrical energy storage technologies. Despite significant advantages for applications in electrochemical devices, the use of solid polymer electrolytes is strongly limited by their poor ionic conductivity. The classical theory predicts that the ionic transport is dictated by the segmental motion of the polymer matrix. As a result, the low mobility of polymer segments is often regarded as the limiting factor for development of polymers with sufficiently high ionic conductivity. Here, we show that the ionic conductivity in many polymers can be strongly decoupled from their segmental dynamics, in terms of both temperature dependence and relative transport rate. Based on this principle, we developed several polymers with "superionic" conductivity. The observed fast ion transport suggests a fundamental difference between the ionic transport mechanisms in polymers and small molecules and provides a new paradigm for design of highly conductive polymer electrolytes. [ABSTRACT FROM AUTHOR]