Two potential liquid fertilizers were produced from two mature “alperujo” composts by using an alkaline extraction (1M KOH at 70°C). The characteristics of the resulting humic‐like substances were compared to those extracted according to the international humic substance society protocol by using elemental analysis, FTIR and fluorescence spectroscopy in both excitation‐emission matrix and synchronous modes. The results obtained confirmed that the hot alkaline extraction dissolved more polymerized compounds, probably including lignin degradation by‐products and/or newly formed aromatic materials. On the other hand, based on fluorescence excitation‐emission matrix results, different Δλ (18, 66, and 100 nm) were selected to provide more information about humic substances in synchronous mode. The results showed that the extracted humic‐like substances presented characteristics close to those of standard humic materials. As a consequence, the alkaline extraction of “alperujo” compost with 1M KOH at 70°C can be used to produce liquid organic fertilizers, thus diversifying the marketable products obtained from “alperujo,” the most abundant by‐product of the Spanish olive‐oil extraction industry. © 2012 American Institute of Chemical Engineers Environ Prog, 32: 1170–1178, 2013