Mono and hetero binuclear cryptates, [Gd(III)ML](+) [M = VO(IV), Co(II), Ni(II), Cu(II)], were synthesized by a 2-step method. The ligand L represents the deprotonated anionic cryptate obtained by the 2+3 condensation of tris-(2-aminoethyl)amine with 2,6-diformyl-4-nitrophenol. The complexes were characterized by elemental analysis, spectral, magnetic, and electrochemical studies. Fluorescence of Gd(III) ion in the cavity was quenched by the encapsulated Cu(II) and Ni(II) ions. [GdCoL(NO3)](+) cryptate had a high lifetime value compared to other cryptates. The cyclic voltammogram showed that the reduction potential values of [Gd(M)L] M = VO(IV), Co(II), Ni(II), and Cu(II) complexes were in the following order: Cu(II) > Ni(II) > Co(II) > VO(IV). The efficiency (eta) of the cryptate based dye-sensitized solar cell (DSSC) increases in the following order: [GdVOL(NO3)](+) < [GdCoL(NO3)](+) < [GdCuL(NO3)](+) < [GdHL] < [GdNiL(NO3)](+).