The effect of several flowering dicotyledonous catch crop plants (dicots) on milk fat quality in cows was investigated to test the hypothesis that their phenolic compounds may inhibit ruminal biohydrogenation and thus enhance the transfer to milk of intact, plant-derived polyunsaturated fatty acids. Berseem clover (Trifolium alexandrinum), buckwheat (Fagopyrum esculentum), and phacelia (Phacelia tanacetifolia) were sown in mixture with ryegrass (Lolium multiflorum; intended biomass proportion of 0.2) on 1ha. For comparison, nonflowering chicory (Cichorium intybus, also sown in mixture with ryegrass) and pure ryegrass were cultivated. Realized biomass proportions (wet weight) were 91% for berseem clover, 69% for buckwheat, 54% for phacelia, and 51% for chicory. At the start of flowering (or from d 47 after sowing onward), cultures were harvested daily and fed for 20 d ad libitum to groups of 6 midlactation cows each. Additionally, 1 kg each of energy and protein concentrate and pure ryegrass hay were fed. Individual intake and milk yield of the cows were measured daily. Milk samples were obtained twice daily 5 d before and from 11 to 20 d after the start of treatment feeding. Feed samples were drawn twice a week from the fresh feeds. Apart from standard traits, feeds and milk were analyzed for fatty acids, tocopherols, and phenolic fractions. Only a few substantial treatment effects on intake and performance were observed. All diets based on dicots increased α-linolenic acid (ALA) concentrations in milk fat compared with the ryegrass diet even though the corresponding swards were not generally richer in ALA. The highest ALA concentration in milk fat (1.3 g/100g of fatty acids) occurred with the berseem clover diet. Transfer rate of ALA from feed to milk was highest with the buckwheat diet (0.09) and lowest with ryegrass (0.05). This was congruent with the differences in total extractable phenols, being high in the buckwheat sward (2.6% of dry matter) and low in the ryegrass sward (1.2% of dry matter). Intermediates of ALA biohydrogenation were lowest in the milk fat of the buckwheat group, indicating an inhibitory effect of this treatment, which provided the highest dietary levels of phenols. The α-tocopherol concentration in milk was higher with the buckwheat diet than with berseem clover and phacelia diets. The study provides evidence that the ALA concentration in milk fat could be enhanced by feeding flowering dicots; however, this was due to different modes of action.