Abstract The two bond length alternation related backbone carbon–carbon stretching Raman active normal modes of polyacetylene are notoriously difficulty to predict theoretically. We apply our new linear/exponential scaled quantum mechanical force field scheme to tackle this problem by exponentially adjusting the decay of the coupling force constants between backbone stretchings based on their distance which extends over many neighbors. With transferable scaling parameters optimized by least squares fitting to the experimental vibrational frequencies of short oligoenes, the scaled frequencies of trans-polyacetylene and its isotopic analogs agree very well with experiments. The linear/exponential scaling scheme is also applicable to the cis-polyacetylene case.