Humic fraction (HF) functional group-type and content are expected to depend on molecular size, which in turn, is expected to influence formation of heavy-metal complexes. In this study, corn (Zea mays L.) stalks and leaves were decomposed for an 8-month period to produce water-soluble humic substances. These substances were separated into three water-soluble fractions, HF1, HF2 and HF3, from highest to lowest relative molecular size. Functional group determination showed that carboxylic, and phenolic OH acidity increased as relative molecular size of humic fractions decreased. We also observed decreasing C/O ratios from larger to smaller corn tissue-derived humic fractions, whereas N/C and H/C ratios remained relatively unaffected. Furthermore, using potentiometric titration and FTIR spectroscopy we studied formation of Ca2+-, Cd2+-, and Cu2+-humic fraction complexes and how they were affected by pH and molecular size. We determined that metal-humic complexes exhibited at least two types of functional group-sites with respect to Ca2+, Cd2+, and Cu2+ complexation. Strength of metal-ion humic complexes followed the order Cu2+ > Cd2+ > Ca2+ and was affected by pH, especially for low affinity sites. Carboxylic groups were most likely the dominant group-sites involved in complex formation. Magnitude of the metal-humic formation constants in the logarithmic form at the lowest equilibrium metal-ion concentration, under the various pH values tested, varied from 5.39 to 5.90 for Ca2+, 5.36 to 6.01 for Cd2+, and 6.93 to 7.71 for Cu2+. Furthermore, the formation constants appeared to be positively influenced by decreasing molecular size of water-soluble humic fraction, and increasing pH. However, our molecular spectra showed that the pKa of corn humic fractions increased with decreasing relative molecular size and that Cu2+ was more covalently bonded by humic fractions than were Ca2+ and Cd2+, and the nature of the covalent bond character was independent of pH.