The paper provides an overview of the various analytical and microanalytical techniques currently in use to characterise the outcomes of pyrometallurgical processes, examining the advantages and limitations of these approaches. Specific focus with be given to quantitative microanalysis techniques including electron probe microanalysis and laser ablation, covering general principles, capabilities and limitations and recent development to address specific challenges associated with analysing molten slag, matte, and alloys, highlighting the necessity of embracing the application of these and other innovative analytical methodologies.