Structure allows you to assign individuals to populations and to determine the extent and sources of genetic admixture in individual multi-locus genotypes, without a-priori specification of groups.
It depends on the basic problem you are addressing. For instance, STRUCTURE gave me important information on genetic stock structure and boundaries for exploted marine species.
STRUCTURE uses assignment methods to cluster individuals according to their genetic similarity. It can be used to study the genetic structure of a group of populations, or between different hybridizing species. For example, it gives an idea of which populations are more connected through gene flow and which ones are more divergent. If it is used together with other analyses such as PCA, can be very useful for population genetics.