Here we report a semiconductor-assisted laser desorption/ionization mass spectrometry (SA-LDI MS) platform to monitor photocatalytic reactions online and apply it for ultrafast reaction screening. In this method, we use photocatalytic nanomaterials as the substrate for LDI and then initiate and monitor the reactions simultaneously. The features of our method include the following: (i) It has a reaction acceleration effect: only seconds are needed in our interfacial reactions vs hours in conventional bulk phase. (ii) The reaction trend in our system agrees with that in bulk phase. (iii) By adding a stable analogue of reactant as internal standard, a quantification of the reaction can be achieved. (iv) The sensitivity is high: for 500 amol of reactant, the photocatalytic reaction can still be initiated and detected. This platform has advantages in ultrafast reaction screening (e.g., screening of nine catalysts requires 24 h by the UPLC-MS system but only 10 min by SA-LDI MS). Furthermore, the high specificity of MS enables the screening of catalytic selectivity of A-TiO2 nanoparticles for a methyl red (MR) and acid yellow (AY) mixture, whose absorption wavelengths are overlapped and thus cannot be discriminated by conventional optical methods. Furthermore, by using SA-LDI MS, we also monitored reductive debrominations during the degradation process of polybrominated diphenyl ethers (PBDEs), which is a type of important pollutant that is difficult to degrade and detect in liquid phase, and the photocatalytic reduction of CO2. Overall, SA-LDI MS realizes ultrafast photocatalytic reaction screening for the first time and provides practical analytical value in the field of catalyst screening.