A detailed analysis of the electronic structure and charge distribution around the trigonal site of Li-doped polyacetylene is reported using finite chain and periodic descriptions of the polymer. Atoms-in-molecules (AIM) analysis is done to characterize the nature of the bond between Li and the polymer backbone through the location of the bond critical points and computation of the total charge on the atomic basins around the doping site. We find that the Li atom donates practically one electron to the π-system, in accordance with the classical Su-Schriffer-Heeger model. However, despite that the Li atom is equidistant from the three closest C atoms in the geometric soliton, a single Li-C bond critical point is found. The AIM quantitative analysis of the electronic density reveals that the Li(+) ion is immersed into the polymer π-cloud in a way that resembles a metallic bonding interaction.