The structure of the microbial food web was studied in six estuary areas along the eastern Adriatic coast during March, July and October 2012. Limitation by phosphorus, not nitrogen, was a common feature for all studied estuaries. Heterotrophic bacteria and autotrophic picoplankton (APP) (particularly picoeukaryotes and Synechococcus) can reach notable abundances and biomasses, suggesting potential importance of the picoplankton community in P-limited estuarine environments. The main features of the microbial community structure in these environments included: (1) higher heterotrophic biomass in comparison to autotrophic biomass within the picoplankton community; (2) general domination of picoeukaryotes within the APP community, and increase of absolute and relative biomass of prokaryotic autotrophs (Prochlorococcus and Synechococcus) in the total APP in P-limited conditions; (3) domination of Synechococcus over Prochlorococcus biomass in all studied conditions, and common spatial distribution of these two groups of cyanobacteria, which was mostly determined by concentration of phosphorus; (4) relatively high contribution (about 50%) of LNA bacteria in the total bacterial abundance; and (5) relatively high contribution (about 33%) of heterotrophic pico-flagellates in the total flagellate abundance.