The microstructural analysis of 1,4-cis- and of 1,4-trans-polymyrcene was conducted by means of thorough investigations at a very high field NMR (21.1T, 900 MHz). A set of 1D and 2D experiments helped to entirely assign the resonances of the spectra for both stereoisomers. A simple method to distinguish between each stereoisomer by NMR spectroscopy is finally provided. (C) 2014 Elsevier Ltd. All rights reserved.