A combined handheld XRF and LIBS system and method includes an XRF subsystem with an X-ray source operated at a fixed medium voltage and configured to deliver X-rays to a sample without passing through a mechanized filter and a detector for detecting fluoresced radiation from the sample. The LIBS subsystem includes a low power laser source for delivering a laser beam to the sample and a narrow wavelength range spectrometer subsystem for analyzing optical emissions from the sample. The X-ray source is operated at the fixed medium voltage to analyze the sample for a first group of elements, namely, transition and/or heavy metals. The low power laser source is operated to analyze the sample for a second group of elements the XRF subsystem cannot reliably detect, namely, C, Be, Li, Na, and/or B, and to analyze the sample for a third group of elements the XRF subsystem cannot reliably detect at the fixed voltage, namely, Al, Si, and/or Mg, or where the XRF subsystem would require higher tube voltage, namely Cd, Ag, In, Sn, Sb, and/or Ba; and/or rare earth elements.