The chemistry of silicon (Si), the second most abundant element in soil after oxygen, is not yet fully understood in the soil-water-plant continuum. Although Si is widely accepted as an element that has little or no interaction with natural organic matter, some data seems to show the opposite. To identify a potential interaction between natural organic matter and Si, batch experiments were achieved at various pH and Si concentrations, involving also Al 3+ as a common ion in soil and using humic acid (HA) as a typical model for natural organic matter. Several complementary techniques were used to characterize the possible complexes formed in the dissolved or solid phases: molecular fluorescence spectroscopy, 29 Si solid-state NMR, Fourier transform infrared spectroscopy, quantification of Si, Al and organic carbon, and nanoparticle size distribution. These tools revealed that humic acid indeed interacts, but weakly, with Si alone. In the presence of Al, however, a ternary complex HA-Al-Si forms, likely with Al as the bridging atom. The presence of Si promotes the maintenance of both Al and DOM in solution, which is likely to modify the result or the kinetics of pedogenesis. Such complexes can also play a role in the control of Al toxicity towards plants and probably also exists with other metals, such as Fe or Mn, and other metalloids such as As.