This review offers the reader a wealth of information published between April 2010 and March 2011 concerning analytical endeavours using the range of conventional and hyphenated XRF techniques that encourage the user to ensure the potential for high spectral sensitivity and, where appropriate, spatial resolution is achieved. The development of advanced micro-beam set ups and new X-ray optics driven by third generation synchrotron based XRF techniques provide nano-imaging and the detection of nano-particles on single cells whilst TXRF coupled with GIXRF and GEXRF offer great potential for non-destructive investigations of thin layers on reflecting surfaces as well as depth profiling of implants. A new portable XRF system is described as an alternative for the traditionally applied K-X-ray fluorescence technology for in vivo measurements of lead in bone. Cryogenic cooling of heat sensitive biological samples is offered as a method to mitigate possible damage by the use of the more powerful μ-XRF technique. Other new preparation methods are also reviewed for the presentation and analysis of industrial, environmental and archaeological samples. One of the more unusual contributions available this year in the characterisation and use of industrial minerals showed that a semi-precious stone, amethyst, is more effective at shielding radiation than concrete.