A survey on the chemical fingerprints and fungal-algal association patterns of Icelandic cetrarioid lichens has revealed that the lichen Cetrariella delisei is unique, in terms of its chemistry and symbiotic association. The depside-producer C. delisei only associates with one algal lineage, while the other related taxa associate with the algae belonging to the “Trebouxia simplex” group. The algal lineage associated with C. delisei turned out to be a new algal clade in parallel to the known four Trebouxia clades (i.e. “A”, “C”, “I” and “S” clades), which was supported by multi-locus phylogenetic analyses. Ultrastructural examinations on axenic algal cultures revealed that the algae do not show a typical pyrenoid morphology and it has pyrenoglobuli distributed across the chloroplast membranes. A new Trebouxia species was therefore described, and we name the algae lineage as the Trebouxia delisei clade (i.e. “D” clade).