Process for treating high-concentration pyridine aqueous solution is carried out by boiling while distilling for high-concentration pyridine aqueous at constant temperature continuously, delivering it to top of tower to obtain pyridine-constant-hydrated boiling substances, circulation utilizing, hierarchical extracting 1-10 times with coarse pyridine biological diesel-oil as extracting solvent at normal temperature, or countercurrent extracting continuously in proportion of solvent: waste water=5:1-1:10 and pH=4-10 for 3-30 mins, laying aside for 5-15 mins, separating, decompress distilling for extracting phase containing pyridine and biological diesel-oil, and recovering pyridine and biological diesel oil. It's simple, economical and has better effect and no environmental pollution.