Two silica reagents based on a 4-hydroxy-3-nitrobenzoyl backbone were synthesized and characterized with 9-fluorenylmethoxycarbonyl (FMOC) and 9-fluoreneacetyl (FA) tags. These reagents were tested by derivatization of primary and secondary amines. Derivatization conditions such as temperature, time and triethylamine catalyst were tested. The FA-tagged silica reagent showed better performance than the FMOC-tagged silica reagent by a comparison of derivatization efficiencies, stabilities of reagents, and blank reagent interferences with derivatization. Finally, cadaverine and an aliphatic amine mixture were analysed using the FA-tagged reagent by pre-column, off-line derivatization and fluorescence detection.