The effectiveness of association mapping (AM) based on linkage disequilibrium (LD) is currently being tested in a number of crops. An important prerequisite for the application of AM is the availability of collections of accessions with a suitable level of genetic variation for target traits and with limited spurious LD due to the presence of population structure. Herein, the results of a genome-wide molecular characterization of a collection of elite durum wheat accessions well-adapted to Mediterranean environments are presented. Ninety-seven highly polymorphic simple sequence repeats and 166 amplified fragment length polymorphism markers were used to characterize 189 durum accessions, mainly cultivars and advanced breeding lines. Genome-wide significant and sizeable LD indices at a centimorgan scale were observed, while LD mainly decayed within 10 cM. On the other hand, effects due to spurious LD were notably lower than those previously observed in a durum wheat collection sampling durum gene pools of more diverse origin. These results, coupled with the high level of genetic variability detected for a number of important morpho-physiological traits and their high heritability, indicate the suitability of this collection for AM studies targeting agronomically important traits.