This chapter highlights the major physical methods, analytical techniques, theoretical and computational methods reported in organophosphorus chemistry research publications during 2012. As in previous years, it has been divided appropriately into eleven main sections and relevant subsections. These are:‐ Theoretical and Computational Chemistry methods, NMR spectroscopy, EPR spectroscopy, Vibrational (IR and Raman) spectroscopy, Electronic (UV‐Visible, Fluorescence, and Luminescence) spectroscopy, X‐ray (XRD) structural studies, Electrochemical (Voltammetry, Sensors and Biosensors) methods, Thermodynamics and Thermochemistry and Thermal methods, Mass spectrometry, Chromatography and related separation techniques (including GC‐MS and LC‐MS), and finally a short section on Kinetics.