In this study, we investigated the effects of hydrothermal temperature on molecular reaction pathways and the plant growth of dissolved organic matters (DOMs) in anaerobic digestion sludge (ADS) via post-hydrothermal treatment (PHT). ADS-derived DOMs mainly comprise lignins/carboxyl-rich alicyclic molecules-like and proteins/aliphatic-like compounds featured with enriched N1-2O6-7 and O8-10 fragments. With the increase in the hydrothermal (HT) temperature, the relative abundance of the compounds with < 7O atoms in DOMs gradually increased in HT-treated samples. Furthermore, based on Fourier transforms ion cyclotron resonance mass spectrometry (FT-ICR-MS)-based reactomics, we found that CHON compounds possessed the highest reactivity, and that reaction of carbonyl (loss of glyoxal (−C2H2O2)) with unique reaction precursors possessed the largest number of high-frequency reactions at different HT temperatures. Consequently, DOM160 contained higher levels of N&O heterocyclic compounds and acetic acid, inhibiting pakchoi growth, and causing an increase in superoxide dismutase activity in the roots. However, DOM200 comprised a higher content of amino acids and humic/fulvic acids, increasing indole-3-acetic acid concentration and H+-ATPase activity in the pakchoi roots, thus exhibiting higher plant activity. Overall, the best HT temperature for ADS dewaterability and the recovery of organic matter was found to be 200 °C. These findings proposed a promising approach for synchronously recycling biostimulants, deep dewatering of ADS via PHT, and further improving the carbon–neutral operation of wastewater treatment plants.