Coal gasification wastewater (CGW) contains several types of aromatic pollutants, which impart high biotoxicity and reduce the quality of anaerobic treatment. Two types of hydrolysis acidification processes, namely microaerobic hybrid reactor (HA-1) and upflow anaerobic sludge blanket reactor (HA-2), were developed for pre-treatment before the anaerobic treatment. The changes in the dissolved organic matter and biotoxicity were investigated to comprehensively understand the degradation process. The results showed that HA-2 coupledwith an anaerobic reactor achieved a 12.3% and 13.4% higher removal efficiency for chemical oxygen demand and total phenols, respectively, compared with the coupled process with HA-1. Furthermore, HA-2 could transform macromolecules into small moleculesmore efficiently and produce fewer intermediates. The coupled process with HA-2 preferentially removed complex aromatic substanceswith absorptionwavelengths of 285 and 254 nm, according to the sequential orders interpreted fromtwo-dimensional correlation spectroscopy. In addition, the results of fluorescence excitation-emission-matrix with regional integration analysis revealed that the contents of typical cyclic compounds in CGW, such as phenolic, heterocyclic, and polycyclic aromatic compounds were remarkably reduced byHA-2. In addition, HA-2 reduced the toxic unit value of CGW by 67.5% and increased the resazurin dehydrogenase activity of the sludge by 37.5% during CGW treatment, thus improving the biotoxicity removal and biodegradability. However, the coupled process with HA-2 did not significantly affect the "indirect estrogenic activity" of CGW. A Pearson correlation analysis indicated that spectral indicators, such as UV254 and Phi(T,n), presented a high positive correlation with the reduction of acute toxicity and organics. (c) 2020 Elsevier B.V. All rights reserved.