This review summarizes results of our recent solid-state NMR investigations on polyunsaturated 18:0-22:6n3-PC/PE/PS and 18:0-22:5n6-PC bilayers. Data on structure and dynamics of the polyunsaturated docosahexaenoyl (DHAn3, 22:6n3) and docosapentaenoyl chains (DPAn6, 22:5n6), investigated at physiological conditions, are reported. Lipid-protein interaction was studied on reconstituted bilayers containing the G-protein coupled membrane receptor (GPCR) rhodopsin as well as on rod outer segment (ROS) disk membranes prepared from bovine retinas. Results reveal surprisingly rapid conformational transitions of polyunsaturated chains and existence of weakly specific interactions of DHAn3 with spatially distinct sites on rhodopsin.