Each year, viticulture generates thousands of tons of vine shoots in the Spanish La Rioja region without an adequate system for their use. This study attempts to increase the value of this residual biomass, mainly for energy generation. To this end, a representative sampling of vine varieties and vineyards in the region was taken and later thermochemically characterized, measuring moisture, ash content percentage, elemental composition and higher heating value (HHV) among all sampled lots. From these tests, only the variety factor of the vine exhibited any statistically significant influence. A correlation has been formulated to express the higher heating value of vine shoots in terms of their elemental composition, obtaining an estimate with a mean absolute error of 1% and a near zero mean bias error. Finally, because the annual amount of vine shoots generated in the La Rioja region is known, the energetic potential of this biomass has been estimated at 1,400,000 GJ per year, and a map is presented to show the energy density of this waste material from each municipality.