Lignin is a poorly characterized polymer and its exact properties vary depending on both the species of the plant and its location within the plant. Three classes of lignins taken from alfalfa stem were examined. The investigation was concentrated on the determination of chemical changes in the lignins during growth and development by the attenuated total reflectance (ATR) infrared (IR) spectrometric technique. The spectrum of permanganate lignin was comparable to that of acid detergent lignin. The main differences were in the different relative absorbance of the peaks. The predominant component of acid detergent lignin and permanganate lignin was guaiacyl-type lignin. The predominant component of Klason lignin was syringyl-type lignin. A comparison between the signals from lignin in different development stages revealed the appearance of new peaks, which are indications of new bonds and changes in the structure of the lignins.