Rapid and sensitive detection of 2,4,6-trinitrotoluene (TNT) and 4-nitrophenol (4-NP) has attracted considerable attention due to their wide applications as nitroaromatic explosive materials. A novel fluorescence method for TNT and 4-NP based on bovine serum albumin functionalized fluorescent gold nanoclusters (BSA Au-NCs) has been developed. The detection probe BSA Au-NCs can be used as a fluorescent probe for the sensitive and selective detection of TNT and 4-NP simultaneously. A good linearity of fluorescence detection using BSA Au-NCs as a fluorescent probe was observed for TNT and 4-NP concentrations in the range of 10⁻⁸–5 × 10⁻⁵ M and 10⁻⁹–5 × 10⁻⁵ M, with a detection limit of 10 nM and 1 nM, respectively. The high specificity of TNT and 4-NP with BSA Au-NCs interactions provided excellent selectivity towards detecting TNT and 4-NP over other relevant nitroaromatic compounds. This system can be applied to test strips to detect TNT and 4-NP with high sensitivity and selectivity. The vapour of TNT and 4-NP can be detected using BSA Au-NCs test paper within 1 min with a detection limit of 10 pM and 1 pM.