Comments on and a key to the 13 Polycoccum species known in Spain are presented, including synopses of their world distributions. Amongst these is P. rubellianae sp. nov., a lichenicolous fungus growing on thalli of Caloplaca rubelliana in eastern Spain (Valencia). It has relatively small ascomata, the lower part pale brown, and also small ascospores which are coarsely verrucose and have a thick gelatinous sheath when young. The new species is associated with a Phoma-like anamorph. The identity and systematic position of P. opulentum requires further study as the name has been applied to different species, and the occurrence of P. marmoratum in Spain is in need of confirmation. The Spanish record of P. arnoldii on Lecania cyrtella probably refers to another yet undescribed species.