The n-3 and n-6 polyunsaturated fatty acid (PUFA) families are essential for important physiological processes. Their major source are marine ecosystems. The fatty acids (FAs) from phytoplankton, which are the primary producer of organic matter and PUFAs, are transferred into consumers via food webs. Mollusk FAs have attracted the attention of researchers that has been driven by their critical roles in aquatic ecology and their importance as sources of essential PUFAs. The main objective of this review is to focus on the most important factors and causes determining the biodiversity of the mollusk FAs, with an emphasis on the key relationship of these FAs with the food spectrum and trophic preference. The marker FAs of trophic sources are also of particular interest. The discovery of new symbioses involving invertebrates and bacteria, which are responsible for nutrition of the host, deserves special attention. The present paper also highlights recent research into the molecular and biochemical mechanisms of PUFA biosynthesis in marine mollusks. The biosynthetic capacities of marine mollusks require a well-grounded evaluation.Biomolecules 2019, 9, 857 2 of 25 consumers and food consumed, and, therefore, FA can be used as efficient and useful biomarkers for the study of trophic interactions between organisms in aquatic ecosystems [5,6].However, information about the endogenous mechanisms of marine invertebrates responsible for synthesis of n-3 and n-6 PUFAs is still being accumulated. Recent researches have shown the potential of some marine mollusks for endogenous synthesis of long chain PUFAs (LC-PUFAs) [7][8][9]. Based on the transcriptome and genome sequences, as well as various publicly available databases, a number of novel fatty acyl desaturases (Fad) and elongations of very long-chain fatty acid (Elovl) genes have been identified from the major orders of the phylum Mollusca, suggesting that many mollusks possess most of the required enzymes for the synthesis of long chain LC-PUFAs [10]. The question whether these findings of the desaturase sequences in invertebrate species really cast doubt on the idea that the organic matter is transferred along the food chains, and thus the existence of trophic links between primary producers and consumers and the relationship of the FA composition of animals and the FA composition of food, are currently under discussion [8].Mollusk FA have attracted the attention of researchers that has been driven by their critical roles in aquatic ecology and in trophic food webs, as well as by their importance as sources of essential FAs with important impacts on human health [11]. Among marine animals, mollusks are especially important as a source of PUFAs (after fish). Many members of the phylum Mollusca, commonly known as clams and snails, are traditional seafood items in human diets, and rich in essential PUFAs. The edible mollusks are commercially harvested and cultured [12]. Marine bivalve mollusks are highly appreciated, partly because of their positive effects on human health ...