Segmented sandwich membrane method of studying stoichiometry and stability constants of ion-ionophore complexes in ion-selective membranes is considered in detail. The experimental data (reported earlier in Russian) concerning complexes of various ions with valinomycin, with H⁺-selective neutral ionophore hexabutyltriamido-phosphate, and with anion-binding neutral ionophore p-hexyl trifluoroacetylbenzoate is presented in a compact form. Advantages of titration technique in the sandwich membrane method (the presence of an internal criterion of reliability, and the possibility of direct determination of complex stoichiometry coefficients) are specially addressed. Biases of the estimates of the constants caused by ion-pair formation in real membranes and by diffusion potential are analyzed by means of computer simulations. The possibility of revealing two coexisting complexes with different compositions is also discussed.