The use of vegetation indices is a fast and efficient method for vegetation monitoring by the use of remote sensing data. Throughout the years, a large number of multispectral vegetation indices have been formulated, each having variable degrees of efficiency in estimating one or more vegetation parameters such as, health status, nutrient or water deficiency, crop yield, vegetation cover fraction, leaf area index, absorbed photosynthetically active radiation, net primary production and above-ground biomass. Additionally some of them also consider atmospheric effects and/ or the soil background for an enhanced retrieval. With the production of biofuels appearing as a partial alleviation of global energy problem, accurate methods of estimating potential available biomass could prove invaluable for the energy budgeting at a national or international level. The paper is looking back in the past at the vegetation indices that have been used for the estimation of biomass, either directly though empirical relationships or through the estimation of other vegetation parameters such as the Leaf Area Index (LAI) and Absorbed Photosynthetically Active Radiation (APAR). This review was performed within the framework of the FP7 funded “Classification of European Biomass potential for Bioenergy using terrestrial and earth observations” (CEUBIOM) project.