AbstractMulti‐ζ Slater‐type orbitals are frequently used in molecular orbital calculations. Master formulae and numerical tables are available in literature for overlap integrals betweens,p, anddatomic orbitals up to principal quantum number (n) = 3 and for some other selected quantum numbers. However, no master formula or numerical table is available for quantum numbersn= 5 and above and involving ƒ orbitals. In this article recursion formulae have been presented for the calculation of the overlap integral between any twos,p,d, and ƒ atomic orbitals formed by a linear combination of Slater‐type orbitals. These formulae, when expanded, would give rise to all the master formulae reported in the literature as well as formulae hitherto un