This research is devoted to the development and study of novel cross-sensitive sensors based on modified extracting ligands. According to the previous results of liquid extraction studies, the chemical modification of membrane active components would change the analytical characteristics of a sensor comprising them. The sensing elements of the studied sensors consisted of various derivatives of N,N,N′,N′-tetraoctyldiamide of diglycolic acid (TODGA) and di-phenyl-N,N-di-i-sobutylcarbamoylmethylen phoshine oxide (CMPO) used as neutral carriers, CCD (chlorinated cobalt dicarbollide) as a lipophilic additive, different plasticizers, and poly(vinyl chloride) (PVC) as a polymer. TODGA-based sensors demonstrated a stable and reproducible response towards rare earth cations in acidic media (pH = 2). Changing the concentrations and ratio of neutral carriers and the lipophilic additive, it is possible to modify the sensitivity and selectivity of the sensors towards the same target ions. Bonded ligands, such as cobalt dicarbollide covalently attached to TODGA and CMPO, exhibited lower selectivity and sensitivity to rare earth cations. A possibility to vary the cross-sensitivity patterns of the sensors in a wide range might be of great interest for the development of multisensor systems allowing the simultaneous determination of several analytes in multicomponent solutions.