Optimizing photovoltaic (PV) devices requires characterization and optimization across several length scales, from centimeters to nanometers. Synchrotron-based micro-X-ray fluorescence spectromicroscopy (μ-XRF) is a valuable link in the PV-related material and device characterization suite. μ-XRF maps of elemental distributions in PV materials have high spatial resolution and excellent sensitivity and can be measured on absorber materials and full devices. Recently, we implemented on-the-fly data collection (flyscan) at Beamline 2-ID-D at the Advanced Photon Source at Argonne National Laboratory, eliminating a 300 ms per-pixel overhead time. This faster scanning enables high-sensitivity (∼1014 atoms/cm2), large-area (10 000s of μm2), high-spatial resolution (<200 nm scale) maps to be completed within a practical scanning time. We specifically show that when characterizing detrimental trace metal precipitate distributions in multicrystalline silicon wafers for PV, flyscans can increase the productivity of μ-XRF by an order of magnitude. Additionally, flyscan μ-XRF mapping enables relatively large-area correlative microscopy. As an example, we map the transition metal distribution in a 50 μm-diameter laser-fired contact of a silicon solar cell before and after lasing. While we focus on μ-XRF of mc-Si wafers for PV, our results apply broadly to synchrotron-based mapping of PV absorbers and devices.