A method was developed for simultaneous determination of 15 amino acids and 7 alkyl amines. The method was based on the employment of high performance liquid chromatography/fluorescence detection and online derivatization with o-phthaldiadehyde. The 22 derivatives were separated within 30 min including the equilibration time and detected by a fluorescence detector at an excitation wavelength of 230 nm and emission wavelength of 450 nm. The analysis procedure was satisfactorily validated by the reproducibility, recovery, linearity and detection limit of the analytes. The relative standard deviations (RSDs) of retention time and peak area for individual amino acids and alkyl amines were consistently less than 0.30% and 2.35%, respectively. Good recovery values ranging from 70% to 109% were obtained. The proposed method showed good linearity (R2≥0.99) in the range of 0.125-125 μM/L for amino acids and 2.5-5000 ng/L for alkyl amines. The detection limit ranged from 0.13 pM to 0.37 pM for individual amino acids and from 0.9 ng to 7.2 ng for individual alkyl amines. The developed and validated method was successfully applied to the quantitative analysis of amino acids and alkyl amines in continental and marine aerosols in China. Among the identified organic nitrogen compounds, 7 amino acids and 6 alkyl amines were detected in every aerosol sample. Glycine was the dominant amino acid, with the average of 130.93 pmol/m3 (accounting for 83% of the total amino acids) and 137.22 pmol/m3 (accounting for 66% of the total amino acids) in continental and marine aerosols in China, respectively. Methylamine and ethanolamine were the most abundant alkyl amines, contributing 87% and 64% to the total alkyl amines in continental and marine aerosols in China, respectively. This work provided an accurate, sensitive and simple method to determine simultaneously amino acids and alkyl amines, and applied the proposed method to the first investigation of amino acids in Shanghai and amino acids and alkyl amines in Huaniao Island in China. The finding of considerable amino acids and alkyl amines in continental and marine aerosols may exert significant implications on nitrogen cycling and atmospheric chemistry.