Combining polycondensation/hydrogenation allowed varying crosslink density in a controlled way. The obtained solvent-free and oligomer-free polymer electrolytes exhibit outstanding conductivities in a wide temperature range. In comparison with poly(oxyethylene) (PEO) based electrolytes, the conductivities of the new crosslinked polymer electrolytes are much higher at ambient temperatures. Furthermore, their conductivity maxima exceed the PEO ones and, to the best of our knowledge, are the highest known. Moreover, contrary to PEO electrolytes, they don’t creep after melting. The unsophisticated architecture and chemistry make easy the scale up of these promising polymer electrolytes.