The effect of humic acid extracted from peat (AHt) on improving the struvite (STR) fertilizing efficiency is explored. To this end, a soil incubation study is correlated to plant assays comparing STR, STR-AHt, and superphosphate (SSP). Characterization techniques confirm the incorporation of the AHt into the STR. The P-pool distribution of STR and SSP is similar in the soil incubation, with STR-AHt presenting a higher labile P at 90 days passing from 10 to 15% P from SSP and STR to 25% P with STR-AHt. However, when applied to barley and tomato, STR yields more shoot P content, aboveground biomass, and residual P in soil than SSP. STR-AHt does not improve the STR results. The poor correlation observed between soil incubation and plant trials highlights the role of the rhizosphere in testing the fertilizer efficiency of STR. Mechanistic assays indicate the key role of rhizosphere pH. Finally, molecular modeling reveals a higher stabilization of STR with AHt, which could reduce P release decreasing the fertilizing potential of STR-AHt, as observed in the pot trials.