This technology provides a temperature-controlled electrospray ionization (ESI) source that allows for highly precise and accurate characterization of the thermal stability and aggregation of proteins by ESI mass spectrometry (MS). The ESI source was designed to eliminate artifacts that interfere with the detection of temperature-induced changes of biopolymer properties. It minimizes biopolymer degradation prior to the analysis, and incorporates a long heat shield to greatly improve thermal control during sample introduction into the ESI interface. This technology, coupled with high specificity of MS detection, enables the study of both reversible and irreversible processes of biopolymers in solution, and allows the early stages of heat-induced protein aggregation to be characterized in detail by monitoring both conformational changes and formation of oligomeric complexes as a function of temperature.