Generalized two-dimensional correlation vibrational spectroscopy is potentially a powerful method for the study of interactions in polymer blends. This paper is the first in a series that systematically examines the utility of this technique and deals primarily with methodology. Normalization methods are discussed, and the effects of concentration errors and small bandwidth variations are considered. These often occur in immiscible systems because of sample preparation problems and lead to features in asynchronous spectra that can be misinterpreted.