We report on the experimental realization of Pb1-xSnx Te pentagonal nanowires (NWs) with [110] orientation using molecular beam epitaxy techniques. Using first-principles calculations, we investigate the structural stability of NWs of SnTe and PbTe in three different structural phases: cubic, pentagonal with [001] orientation and pentagonal with [110] orientation. Within a semiclassical approach, we show that the interplay between ionic and covalent bonds favors the formation of pentagonal NWs. Additionally, we find that this pentagonal structure is more likely to occur in tellurides than in selenides. The disclination and twin boundary cause the electronic states originating from the NW core region to generate a conducting band connecting the valence and conduction bands, creating a symmetry-enforced metallic phase. The metallic core band has opposite slopes in the cases of Sn and Te twin boundaries, while the bands from the shell are insulating. We finally study the electronic and topological properties of pentagonal NWs unveiling their potential as a new platform for higher-order topology and fractional charge. These pentagonal NWs represent a unique case of intrinsic core-shell one-dimensional nanostructures with distinct structural, electronic and topological properties between the core and the shell region. (a) Scanning transmission electron microscopy image of a pentagonal nanowire; the inset shows the disclination and core chain (CC). The red bands from the core connect the valence and conduction bands for (b) cation and (c) anion twin-boundaries.