Plants are well known for producing a wide diversity of natural compounds and several strategies have been proposed to enhance their production. Among them, somatic chromosome doubling may represent an effective and inexpensive method. The objective of the current study was to investigate the effect of polyploidization on the leaf metabolic profile and content of tetraploids produced from a wild diploid (2n=2x=24) potato species, Solanum bulbocastanum Dun. Photochemical efficiency of tetraploids was also analyzed. Results from HPLC-DAD and LC/MS analyses provided evidence that tetraploid genotypes displayed either a similar or a lower phenylpropanoids, tryptophan, tyrosine and a-chaconine content compared with the diploid parent. Similarly, no significant differences were found among genotypes both for measures of gas and for chlorophyll fluorescence, except for non-photochemical quenching (NPQ). Steroidal saponins content revealed superiority of some tetraploids with respect to the diploid parent, suggesting perturbations in the mechanism regulating the biosynthesis of such compounds following polyploidization. Lack of superiority may be attributed to the time required for adjustment, adaptation and evolution after the genomic shock induced by polyploidization, as well as the fact that an optimum ploidy level for each species may be crucial. Our results suggest that polyploidization as a strategy to enhance metabolite production cannot be generalized.