The section of the Liguro-Provencal basin north of the Balearic Islands is one of the most productive sites in the whole Mediterranean Sea, with intense phytoplankton bloom lasting about 2 months in late winter-early spring. The phytoplankton species composition of the area was investigated using light and electron microscopy to analyze bottle and net samples collected at several stations in spring 2000 and 2003. Serial dilution cultures established from bottle samples were also examined. A total of 168 phytoplankton taxa was identified, consisting of 73 Coscinodiscophyceae, 47 Dinophyceae, 25 Coccolithophyceae and 4 Prymnesiophyceae, 5 Prasinophyceae, 3 Chrysophyceae, 2 Cryptophyceae, 2 Dictyochophyceae, 1 Euglenophyceae, 1 Pelagophyceae, 1 Choanoflagellidea, 1 Filosea and 3 incertae sedis. We also provided a brief taxonomic description and original micrographs for 25 of the smallest and/or less known species identified in the study area, which may go undetected during routine microscopical analysis of fixed samples. Among these, 10 species were recorded for the first time in the Mediterranean Sea, confirming the need of detailed studies to reveal the biodiversity and biogeography of Mediterranean phytoplankton.