Application of a general and convenient approach to the synthesis of heteronuclear crown-substituted triple-decker phthalocyaninates afforded two series of complexes containing one dia- and one paramagnetic Ln(III) ion (for Y and almost the whole lanthanide family), [(15C5)(4)Pc]-M*[(15C5)(4)Pc]M(Pc) (or [M*,M] for brevity sake), where (15C5) is 1S-crown-5; (Pc2-) is phthalocyaninato dianion; and M not equal M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This approach consists of using LaPc2 as an efficient Pc2- source. The solid-state structures of two complexes ([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction analysis, providing therefore a structural model for the assignment and analysis of H-1 NMR spectra of the complexes, which is strongly affected by the presence of paramagnetic lanthanide ions. Model validation was performed on complexes containing two different paramagnetic ions-[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm] and [Tm*,Tb]-synthesized by the above-mentioned method.