Surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF) combined emissions were used in this work to the analysis of humic acids (HA). This study examined HA structure at different pH and HA concentrations and assessed the structural differences taking place in HA as a result of various amendment trials. Raman and fluorescence emissions behave in opposite ways due to the effect of the metal surface on the aromatic groups responsible for these emissions. The information afforded by these techniques can be successfully employed in the structural and dynamic analysis of these important macromolecules. The surface-enhanced emission (SEE) spectra, that is the sum of the Raman and the fluorescence emissions, were acquired by using both macro- and micro-experimental configurations in order to apply imaging and confocal Raman and fluorescence spectroscopy techniques on the analysis of HA.