The absorbance changes that occur when the mole ratio of the components of ligand complex equilibria is varied while the concentration of one component is kept constant (mole ratio method) allow evaluating stability constants in favourable conditions. Values of the corresponding stability (association) constants are normally assigned on the basis of spectrophotometric analysis. Determination of stability constants can be performed by a number of linear procedures, but most of these, suffer from theoretical and practical drawbacks, e.g., linear transformation of the rectangular hyperbola type of binding constants, is valid only when one of the two species is present in a large excess. A rigorous treatment of the experimental mole ratio data for 1:1 weak complexes is carried out in this paper with the aim of eliminating some of the assumptions involved in the other methods usually applied for evaluating stability constants. Orthogonal regression is required in order to take into account the error in both axes. The method has been applied to literature data for the iron(III)-thiocyanate and nickel(II)-selenocyanate systems, as well as to a number of host–guest cyclodextrin complexes.