The current study introduces groundbreaking insights into how organic matter (OM) of the black phosphate (RB-Ph) uniquely influences phosphorus (P) solubility during acetic acid (AA) leaching, expanding our understanding in this crucial area. To highlight such role, the OM of the RB-Ph was treated separately by different procedures including calcination at 550 ℃/4 h (CB-Ph), 30% hydrogen peroxide (HB-Ph) and intensive grinding to nano-sizes (NB-Ph). The mineralogical, chemical and morphological characteristics of phosphatic and non-phosphatic components of these phosphatic materials were carefully examined pre- and post-treatment via different techniques. The P dissolution of the precursor RB-Ph and its modified derivatives all over the applied experimental parameters traced the following trend: NB-Ph > RB-Ph > CB-Ph > HB-Ph. Intensive grinding to nanoscale resulted in amorphous components with conspicuous OM content (TOC, 0.410%), significantly enhanced P dissolution rate of NB-Ph (730–980 ppm), despite the noticeable reduction in its P2O5 content to 22.34 wt.%. The precursor RB-Ph, thanks to its high OM content (TOC, 0.543%), also displayed a sufficient P dissolution rate (470–750 ppm) compared to the two other modified derivatives, CB-Ph (410–700 ppm) and HB-Ph (130–610 ppm). Such deep and conspicuous impact of OM on P solubility can be tied to their decomposition, releasing not only organic acids but also the adsorbed P by the OM’s surficial binding sites to the solution. Finally, the optimum conditions of P leaching were attained at 2:1 acid/solid (w/w) ratio and 2 h of retention time of all investigated samples.