In this study, we found that when Pseudomonas mendocina NK-01 accumulated intracellular carbon reserve, medium chain length poly (3-hydroxyalkanoates), it also synthesized extracellular saccharides, alginate oligosaccharides. The high carbon nitrogen ratio of culture medium facilitated alginate oligosaccharides production. We analyzed the structure of alginate oligosaccharide by Ultraviolet-Visible Spectrophotometry, Fourier Transform Infrared Spectroscopy, 1H and 13C of Nuclear Magnetic Resonance, and found that it was compounded in line from β-D-mannuronic acids and α-L-gluronic acids via β-(1→4)/ α-(1→4) bonds, which acetylated partly on the 2- and/or 3-hydroxy. In addition, we determined the weight-average molecular weight of alginate oligosaccharides by gel permeation chromatography to be 2054.