Low-density lipoprotein (LDL) was modified with copper ions (Cu2+) and malondialdehyde (MDA), and the differences were compared. The results show that both oxidative and MDA modification produce a decrease in free amino groups in LDL and enhance its electrophoretic mobility on agarose gel, and that these observations are linked. However, differences produced by the two forms of modification were observed. Oxidative modification of LDL involves free radical-mediated lipid peroxidation which produces large amounts of thiobarbituric acid-reactive substances (TBARS) and conjugated dienes. In addition, vitamin E was reduced considerably and cholesterol lowered, and apolipoprotein B (apo B) fragmentation and aggregation were seen. Similar changes were not seen with MDA modification which does not involve lipid peroxidation. Fluorescence emission spectra of both forms of modified LDL show that emission intensity increases gradually as the modification progresses, but maximum emission wavelength and spectrum patterns are not the same. These findings may be of some significance in the study of the antigenicity, scavenger receptor multiplicity and toxic effects of modified LDL.