The configurations of (6'R)-β,ε-carotene, (3'R,6'R)-β,ε-caroten-3'-ol (α-cryptoxanthin), (3R,3'R,6'R)-β,ε-carotene-3,3'-diol (lutein), (3R)-β,β-caroten-3-ol (β-cryptoxanthin), (3R,3'R)-β,β-carotene-3,3'-diol (zeaxanthin) and all-trans (3S,5R,6S,3'R)-5,6-epoxy-5,6-dihydro-β,β-carotene-3,3'-diol (antheraxanthin) were established by CD and ¹H NMR studies. The red algal carotenoids consequently possessed chiralities at each chiral center (C-3, C-5, C-6, C-3', C-6'), corresponding to the chiralities established for the same carotenoids in higher plants. Two post mortem artifacts from Erythrotrichia carnea were assigned the chiral structures (3S,5R,8R,3'R)-5,8-epoxy-5,8-dihydro-β,β-carotene-3,3'-diol [(8R)-mutatoxanthin] and (3S,5R,8S,3'R)-5,8-epoxy-5,8-dihydro-β,β-carotene-3,3'-diol [(8S)-mutatoxanthin]. This is the first well documented report of a naturally occurring β,ε-caroten-3'-ol (¹H NMR, CD, chemical derivatization).