The improvement of maize double cropping has become increasingly important in recent years. In order to establish breeding programs for sustainable maize production, the goals of the research were (i) to understand the correlations between grain and stover yield and saccharification efficiency, and (ii) to identify QTL and metabolic pathways to design of breeding programs in a double exploitation approach. We carried out a genome-wide association study (GWAS) and a metabolic pathway analysis using a panel of highly diverse maize inbreds. As results, we have obtained that the regulation of energetic and developmental pathways have been pointed out as key pathways related to stover quantity and utilization, while no specific pathways could be identified in relation to grain yield. However, due to the moderate high heritability of yields and their positive correlation a phenotypic selection approach would be adequate for the improvement of both yields, while for saccharification efficiency improvement upcoming genomic selection models are more advisable. Overall, breeding strategies that manage the dual use of maize are viable and will contribute to a more sustainable maize crop in the near future.