The presented study focused on the possibility of using alkaline deep eutectic solvents (ADESs) as green extractants for the isolation of humic substances (HSs) from peat and lignite in a process intensified by ultrasound. For this purpose, the extraction procedure was statistically described on the basis of the Box−Behnken design, and the carboxyl group content in the obtained products was optimized due to the ADES composition, ultrasound intensity, and extraction time. For optimal extraction conditions, the experimental carboxyl content in the isolated products was equal to 3.71 and 2.96 mmol g −1 for the HSs extracted from peat and lignite, respectively. These values were similar to the results for the reference samples, which were HSs extracted using 0.1 M NaOH, as well as humic acids and sodium humates purchased from Sigma-Aldrich. The qualitative assessment of the products obtained was based on spectroscopic methods, including FTIR, 1 H NMR, and UV−vis. The analyses carried out for the isolated samples revealed the characteristic structures of HSs, including components of aliphatic chains and aromatic core as well as carboxyl, ester, and amino groups. Simultaneously, the results of the spectral ratio of E 280 /E 472 showed the significant differences between the relative amount of lignin for the samples tested.