Leprocaulon inexpectatum is described here as a new lichen species and the fourth member of the genus known from Europe. It is characterized by the crustose-granulose, blue-grey to bluish green thallus composed of ±discrete, soredia-like granules c. 45–70 μm in diameter, and the production of usnic acid and zeorin. Based on ITS rDNA, the lichen is closely related to the saxicolous American species L. beechingii. The new species is reported here from numerous localities in north-western Italy. It occurs on the bark of oaks, chestnut, and black locust in open deciduous forests, often in floodplain ecosystems. Our investigation of its photobiont identity using ITS, 18S and rbcL demonstrated that its symbiotic partner represents an undescribed species within the genus Symbiochloris (Trebouxiophyceae). We provide an identification key to sterile crustose sorediate lichens containing usnic acid and zeorin found in Europe.