Twelve different microcrystalline insulin formulations were investigated by X-ray powder diffraction and were shown to have very characteristic patterns. Three of the formulations crystallize in the same crystal system, but have structural differences in the N-terminal B-chain of the insulin molecule. This difference was efficiently detected in the powder patterns. The sensitivity of the method makes it a valuable tool for characterization of microcrystalline samples. By use of principal-component analysis, the twelve different formulations originating from six different crystal systems were classified into nine separate clusters. The powder patterns of each cluster can now be used as `fingerprints' for the different insulin polymorphs. The combination of X-ray powder diffraction and multivariate analysis, such as principal-component analysis, provides a rapid and effective tool for studying the influence of derivatives, additives, ions, pHetc., in the crystallization media.