Phosphorus derivatives with six substituents at the immediate periphery of the heteroatom are quite common,more than usually imagined, and this review presents some of the novel structures that have been reported in the last 5–10 years.Many derivatives of varied charge and geometry have been synthesized in studies devoted to phosphorus reactivity. A large number of compounds have also been prepared for applications in fields as varied as: (i) classical organic chemistry, (ii) stereoselective synthesis and analysis, (iii) bioorganic chemistry, (iv) electrochemistry, and (v) photochemistry. Selected examples of applied transformations, industrial and academic, have been selected to present a general overview of the new trends in P(VI) chemistry.