Longwave radiation components, including downward, upward, and net longwave radiation (DLR, ULR, and NLR, respectively), are essential parameters in heat flux exchange across the ocean–atmosphere interface. However, few long-term, high-resolution, and accurate sea–surface longwave radiation (SSLR) products are available. We generated the first high-resolution (5-km) all-sky daily SSLR product from Advanced Very High-Resolution Radiometer (AVHRR) top-of-atmosphere observations, combined with the European Center for Medium-Range Weather Forecasts Reanalysis V5 near-surface meteorological variables and National Oceanic and Atmospheric Administration sea–surface temperatures from 1981 to 2018. We coupled the densely connected convolutional neural network and bidirectional long short-term memory neural network as a retrieval algorithm. The training dataset was generated using integrated SSLR samples from 2002 to 2012 at 437 globally distributed locations. The archived product, SSLR_AVHRR, showed a high accuracy against 81,546 buoy-based observations from eight observation networks, with an R2 of 0.96 (1.00, 0.77), root mean square error of 10.27 (4.51, 9.27) Wm−2, and mean bias error of −1.30 (0.30, −0.72) Wm−2 for DLR (ULR, NLR) retrievals. Based on SSLR_AVHRR, the global DLR (ULR) flux exhibited a significantly (p-value < 0.05) increasing trend of 1.03 (1.08) Wm−2/decade during 1982–2018. The trend was 0.24 (0.34) Wm−2/decade during 1982–2000, which increased to 1.79 (1.45) Wm−2/decade during 2001–2018. This globally increasing trend was dominantly impacted by the significant increases in high latitude, particularly in the Arctic Ocean. Trend variations at low latitudes, which were more frequent than at middle and high latitudes because of the El Niño-Southern Oscillation, mitigated the increasing rates of global DLR and ULR after strong El Niño years, whereas the global NLR flux remained relatively stable throughout the study period. This method can be extended and applied to estimate other air-sea fluxes based on a unified estimating framework to help mitigate imbalanced energy and freshwater budgets at the air-sea interface to some degree.