The rule of base pairing, which describes how nitrogenous bases pair in the structure of DNA, was primarily established by James Watson and Francis Crick in 1953 as part of their discovery of the double-helix structure of DNA. Their model showed that adenine (A) pairs with thymine (T), and cytosine (C) pairs with guanine (G).
However, the foundational work that led to this discovery involved several scientists, including Erwin Chargaff, whose observations of base ratios in DNA were crucial for formulating the base pairing rules. Chargaff's rules stated that in any given DNA molecule, the amount of adenine equals thymine and the amount of cytosine equals guanine. This provided key insights that Watson and Crick used to propose the double-helix model of DNA.