The complexes formed between Ca2+ and fulvic acid extracted from sewage sludge were investigated by potentiometric titration of K/H‐fulvate with Ca(NO3)2 at pH 7 and 25°C, in an ionic medium of 0.1N KNO3. Formation functions, giving the number of moles of Ca bound per mole of K/H‐fulvate, were calculated from the titration data and plotted against the concentration of Ca2+, with the concentration of K/H‐fulvate being a fixed parameter for each plot. The molarity of K/H‐fulvate, which was held rigorously constant during each titration, was determined with the help of separate experiments in which the number‐average molecular weight of the K/H‐fulvate sample employed was measured by vapor pressure osmometry. The formation functions were interpreted as evidence of: (i) a relatively strong ion pair that is formed between Ca2+ and the most acidic functional groups in fulvic acid, and (ii) a weaker ion pair that is formed between Ca2+ and the more weakly acidic functional groups. The properties of the latter complex depend both on pH and on the concentration of fulvic acid, since these variables in part determine the number of ionized, weakly acidic functional groups that can react with Ca2+. The Ca2+ ion was shown to have a modest ability to displace protons from undissociated acidic functional groups in sludge‐derived fulvic acid.