We examined the association of fatty acid (FA) composition in serum phospholipids with the features of metabolic syndrome (MetS) and arterial stiffness.Korean men (n = 593, 30-79 yrs) were categorized based on the number of MetS risk factors (RFs) and measured for the markers of MetS, serum phospholipid FA composition and brachial-ankle pulse wave velocity (baPWV), an index for the severity of arterial stiffness.Insulin resistance (HOMA-IR), baPWV, LDL size, and adiponectin were significantly altered corresponding to the number of MetS RFs. The proportions of total monounsaturated FA, palmitoleic acid (16:1), oleic acid (18:1ω-9) and dihomo-γ-linolenic acid (DGLA, 20:3ω-6) in serum phospholipids, and DGLA/linoleic acid (LA) (20:3ω-6/18:2ω-6), deta9-desaturase activity (D9D-16: 16:1/16:0 and D9D-18: 18:1ω-9/18:0) significantly increased corresponding to the number of MetS RFs, but D5D (20:4ω-6/20:3ω-6) decreased. baPWV positively correlated with HOMA-IR, palmitic acid (16:0), oleic acid, D6D (18:3ω-6/18:2ω-6), DGLA/LA and D9D-18, and negatively with adiponectin, LDL size, LA, docosahexaenoic acid (DHA, 22:6ω-3) and D5D. Multiple stepwise regression models revealed that baPWV was significantly influenced by systolic blood pressure, age, body weight, triglyceride and LA in serum phospholipids (R(2) = 0.378). Interestingly, baPWV (1419 ± 1 cm/s) and MetS (22%) were highest in individuals with lower proportion of LA (12.361%) and higher proportion of DGLA (≥ 1.412%) in serum phospholipid FAs.The features of MetS significantly related to serum phosopholipid FA composition. Particularly, arterial stiffness was associated with LA additively together with DLGA. It may suggest a potential benefit of sufficient amounts of LA in serum or in diet can reduce cardiovascular risk.