Described here are &Dgr;4 desaturases that convert all-cis-7,10,13,16,19-docosapentaenoic acid [“DPA”; 22:5 ω-3] to docosahexaenoic acid [“DHA”; 22:6 ω-3], with secondary activity in converting docosatetraenoic acid [“DTA”; 22:4 ω-6] to all-cis-4,7,10,13,16-docosapentaenoic acid [“DPAn-6”; 22:5 ω-6]. Also, described here are isolated nuclei acid fragments and recombinant constructs comprising such fragments encoding &Dgr;4 desaturases as well as methods of making long chain polyunsaturated fatty acids [“PUFAs”] using this &Dgr;4 desaturase in oleaginous yeast.