The Arctic climate strongly affects phytoplankton production and biomass through several mechanisms, including warming, sea ice retreat, and global atmospheric processes. In order to detect the climatic changes in phytoplankton biomass, long-term variability of chlorophyll a (Chl-a) was estimated in situ with the changes in the surface sea temperature (SST) and salinity (SSS) in the Barents Sea and adjacent waters during the period of 1984–2021. Spatial differences were detected in SST, SSS, and Chl-a. Chl-a increased parallel to SST in the summer-autumn and spring periods, respectively. Chl-a peaks were found near the ice edge and frontal zones in the spring season, while the highest measures were observed in the coastal regions during the summer seasons. SST and Chl-a demonstrated increasing trends with greater values during 2010–2020. Generalized additive models (GAMs) revealed that SST and Chl-a were positively related with year. Climatic and oceanographic variables explained significant proportions of the Chl-a fluctuations, with six predictors (SST, annual North Atlantic Oscillation index, temperature/salinity anomalies at the Kola Section, and sea ice extent in April and September) being the most important. GAMs showed close associations between increasing Chl-a and a decline in sea ice extent and rising water temperature. Our data may be useful for monitoring the Arctic regions during the era of global changes and provide a basis for future research on factors driving phytoplankton assemblages and primary productivity in the Barents Sea.