The Arctic warming leads to a decline in sea-ice extent and thickness, rapid warming and freshening of the sea surface which impact the distribution of phytoplankton size composition. Picophytoplankton is an ecologically important component of Arctic pelagic marine ecosystems, and its role may be altered by global warming. In this study, the abundance and biomass, the chlorophyll a (Chl-a) and primary production (PP) of picophytoplankton, and its spatial and temporal distribution were investigated in the Kara Sea during the ice-melt season in July 2019. Picophytoplankton played a major role in the surface PP in the southern and western areas of the Kara Sea. In the surface layer, the contribution of picophytoplankton to total Chl-a increased insignificantly, and the contribution of picophytoplankton to total PP decreased significantly with the time of sea ice retreat. In the euphotic zone, the Chl-a concentration of picophytoplankton and its contribution to total Chl-a decreased with the time of sea ice retreat. The average picophytoplankton biomass determined in the present study (2.72 ± 5.10 mg C m−3) corresponded to the biomass estimates in the Arctic. The picophytoplankton community was strongly dominated by eukaryotes, cyanobacteria were only detected at 3 out of 11 stations, with maximum abundances (0.07 × 109 cells m−3) observed at depths below 15 m. The obtained results contribute significantly to the study of the picophytoplankton dynamics during the ice-melting season in the hard-to-reach Kara Sea.