Genera of the Orobanchaceae family are holoparasites that parasitize various hosts. Several members of this family cause severe damage to diverse crop plants. While the biological and life cycles of these parasites have been studied, their metabolism has received little attention, most of which focused on Egyptian broomrape [Orobanche aegyptiaca Pers.; syn.: Phelipanche aegyptiaca (Pers.) Pomel]. This study aimed at obtaining more knowledge about the primary metabolic profiling of four parasite species belonging to the Orobanchaceae family—sunflower broomrape (Orobanche cumana Wallr.), Orobanche cernua, P. aegyptiaca, and branched broomrape [Orobanche ramosa L.; syn.: Phelipanche ramosa (L.) Pomel.]—that developed on tomato (Solanum lycopersicum L.) as a host. Gas chromatography–mass spectrometry analysis demonstrated that significant differences in metabolite content occur between species belonging to Orobanche compared with those belonging to Phelipanche. This finding adds another layer to the separation of these two genera in addition to morphological separation. Moreover, each of these four species exhibits different metabolic profiles, indicating that the parasites can absorb the host's metabolites but also have the ability to self-regulate their metabolites in order to grow and develop.