Dataset related to 'Three-component assembly of multiply-substituted homoallylic alcohols and amines using a flow chemistry photoreactor'. Including 1H, 13C and 19F NMR files (.fid) as well as crystal structure file of compound 4a (.cif). The number of the folders, e.g. 4a, 4b, indicates the compound number in the manuscript. The name of the subfolders, e.g. 1H, 13C, indicates the revelant NMR file. Each individual file is directly generated and exported from Bruker NMR spectrometer. Subfolders could be imported, as a whole, to NMR softwares such as TopSpin or MestReNova, where they could be fully resolved into the corresponding NMR spectrum.