The structure and chemistry of two electrical trees (designated Tree A and Tree B) grown in low density polyethylene have been studied by a combination of confocal Raman microprobe spectroscopy, optical microscopy and scanning electron microscopy. Despite being grown under similar conditions (A, 30 °C and 13.5 kV; B, 20 °C and 13.5 kV), these two trees exhibit very different structures. Tree A exhibits a branched structure while Tree B is more bush-like. In Tree A, the very tips of the structure are made up of hollow tubules, which exhibit just the Raman signature of polyethylene. On moving towards the high voltage needle electrode, fluorescent decomposition products are first detected which, subsequently, are replaced by disordered graphitic carbon. From the relative intensity of the graphitic sp2 G and D Raman bands, the constituent graphitic domains are estimated to be ∼4 nm in size, which leads to a local tree channel resistance per unit length of 1–10 Ω µm−1. These structures are therefore sufficiently conducting to prevent local electrical discharge activity. In Tree B, the observed fluorescence increases continuously from the growth tips to the needle. Here, the tree channels are not sufficiently conducting to prevent electrical discharge activity within the body of the tree. These results are discussed in terms of mechanisms of tree growth and, in particular, the chemical processes involved.