[en] Highlights: • The work spans areas of theoretical physics, polymer characterisation and processing and contributes new insights to scanning electron microscopy based polymer spectroscopy and microscopy. • We investigate the feasibility of using secondary electron spectra as a novel tool for polymer characterization studying P3HT, a widely used material in organic electronics. • We present a Monte Carlo modeling method that can be used to explore Secondary Electron Spectra and Secondary Electron emission for P3HT and other polymer materials. - Abstract: The nano-scale dispersion of ordered/disordered phases in semi-crystalline polymers can strongly influence their performance e.g. in terms of mechanical properties and/or electronic properties. However, to reveal the latter in scanning electron microscopy (SEM) often requires invasive sample preparation (etching of amorphous phase), because SEM usually exploits topographical contrast or yield differences between different materials. However, for pure carbon materials the secondary spectra were shown to differ substantially with increased order/disorder. The aims here is to gain an understanding of the shape of secondary electron spectrum (SES) of a widely used semi-crystalline polymer regioregular poly(3-hexylthiophene-2,5-diyl), commonly known as P3HT, and its links to the underlying secondary electron emission mechanisms so SES can be exploited for the mapping the nano-morphology. The comparison of simulated and experimental SES shows an excellent agreement, revealing a peak (at about 0.8 eV) followed by a broad shoulder (between 2 eV and 4.5 eV) with respective relative intensities reflecting order/disorder.