Recent instrumentation developments have improved spatial resolution and decreased acquisition times in x-ray photoelectron spectroscopy (XPS). Rapid image acquisition has transformed laboratory XPS imaging from a novelty to an increasingly routine analysis method for surface chemical characterization on the scale of microns. The combination of high spatial and high energy resolution XPS enhances analysis of heterogeneous samples ranging from microelectronic materials to fossils. This enhanced chemical characterization of heterogeneous samples comes at the cost of increasing complexity in the XPS data sets acquired. Spectra-from-images data sets, and imaging series, can produce complex data structures that are not readily interpreted by visual inspection alone. A variety of multi-variate analysis methods can be utilized to facilitate analysis of multi-dimensional data sets, and several examples will be shown. Conclusions based on visual inspection versus principal components analysis will be discussed. New opportunities for multi-technique correlations also arise from the improved spatial resolution and decreased acquisition times. A variety of techniques, including FTIR, AFM and confocal microscopy have fields-of-view which are comparable to imaging XPS, making correlative analyses possible. Data from multi-component polymer samples will be used to demonstrate the direct correlation of XPS images with other imaging methods. This work has been partially supported by NSF ALCOM (DMR89-20147) and NSF CHE-0113724.