The intermolecular distributions of amide groups within two commercial LMA pectins was studied after removal of the methyl esters followed by fractionation of the different populations by anion exchange chromatography. The populations obtained had almost equal degrees of amidation while the values of the degree of blockiness were not the same, indicating also a different intramolecular distribution of the substituents considered as semirandom. Populations from the methyl-esterified amidated pectins showed a rather random distribution for almost all populations. A striking difference between these different populations was that, despite the same level of substitution, the ratio between amide groups and methyl esters varied significantly, indicating a heterogeneous amidation process.