A combination of synchrotron radiation (SR) micro X-ray fluorescence (μ-XRF) and XRF mode X-ray absorption near edge structure (XANES) measurements at the Cr K-edge already allowed us to establish that the photo-reduction of chromates to Cr(III)-compounds is the cause of darkening of chrome yellow pigments (PbCr1-xSxO4, 0≤x≤0.8) in a number of paintings by Vincent van Gogh and in corresponding artificially aged paint models. A silicon drift detector (SDD) was employed to record the Cr-K XRF radiation in these X-ray micro beam-based measurements. However, in view of the limited count rate capabilities and collection solid angle of a single device, µ-XRF and µ-XANES employing single element SDDs (or similar) are primarily suited for collection of spectral data from individual points. Additionally, collection of XRF maps via point-by-point scanning with relatively long dwell times per point is possible but is usually confined to small areas. The development of the 384 silicon-diode array Maia XRF detector has provided valuable solutions in terms of data acquisition rate, allowing for full-spectral (FS)-XANES imaging in XRF mode, i.e., where spectroscopic information is available at each pixel in the scanned map. In this paper, the possibilities of SR Cr K-edge FS-XANES imaging in XRF mode using the Maia detector is examined as a new data collection strategy to study the speciation and distribution of alteration products of lead chromate-based pigments in painting materials. The results collected from two micro-samples taken from two Van Gogh paintings and an aged paint model show the possibility to perform FS-XANES imaging in practical time frames (from several minutes to a few hours) by scanning regions of the same order size of samples (more than 500 µm). The sensitivity and capabilities of FS-XANES imaging in providing representative chemical speciation information at the microscale (spatial resolution from ~2 to 0.6 µm) over the entire scanned area are demonstrated by the identification of Cr(OH)3, Cr(III)-sulfates and/or Cr(III)-organometallic compounds in the corresponding phase maps, as alteration products. Comparable Cr-speciation results were obtained by performing equivalent higher spatial resolution SR µ-XRF/single point µ-XANES analysis using a more conventional SDD from smaller region of interest of each sample. Thus, large area XRF mode FS-XANES imaging (Maia detector) is here proposed as a valuable and complementary data collection strategy in relation to “zoomed-in” high resolution µ-XRF mapping and single point µ-XANES analysis (SDD).