The unbundling of the electricity power system will play a key role on the deployment of distributed generation (DG) in European distribution systems evolving towards Smart Grids. The present paper firstly reviews the relevant European Union (EU) regulatory framework: specific attention is paid to the concept of unbundling of power distribution sector in Europe. Afterwards, the focus is on the current state of penetration of DG technologies in the EU Member States and the corresponding interrelations with distribution features. A comparison between the unbundling of the distribution and supply markets using econometric indicators such as the Herfindahl–Hirschmann (IHH) and the Shannon–Wiener (ISW) indices is then presented. Finally, a comparative analysis between these indices and the current level of penetration of distributed generation in most EU is shown; policy recommendations conclude the paper.