Mass spectrometry is routinely used for myriad applications in clinical, industrial, and research laboratories worldwide. Developments in the areas of ionisation sources, high-resolution mass analysers, tandem mass spectrometry, and ion mobility have significantly extended the repertoire of mass spectrometrists, however for coordination compounds and supramolecules, mass spectrometry remains underexplored and arguably underappreciated. Here, the reader is guided through different tools of modern electrospray ionization mass spectrometry that are suitable for larger inorganic complexes. All steps, from sample preparation and technical details to data analysis and interpretation are discussed. The main target audience of this tutorial are synthetic chemists as well as technicians/mass spectrometrists with little experience in characterising labile inorganic compounds