The cultivation of bioenergy crops could be considered as sustainable; however, its use in fertile lands could conflict with food production. The general purpose of this study is to identify areas where traditional food crops are not economically sustainable, but where they could be substituted by energy crops without changing the land use in Spain. We studied the profit margin of the main crops of the country, which are wheat (Triticum aestivum L.) and barley (Hordeum vulgare L.), the spatial location of the growing areas, and the biophysical constraints. Spain has an extended area of 9.93 million hectares, with biophysical and/or economic constraints in rainfed arable areas. Grain yields ≤1.5 Mg ha−1 are not profitable; low organic matter content is the principal biophysical constraint. The average results showed a potential of 83.33 GJ ha−1 using triticale (x Triticosecale) and 174.85 GJ ha−1 using cardoon (Cynara cardunculus L.) in arable marginal lands. The production of biomass in this area would serve to cover between 3%–5% of primary energy needs in Spain for triticale or cardoon. In this respect, establishing energy crops in marginal lands could be an instrument to enhance rural development, boost the bio-economy, and reach environmental targets.