A linear trinuclear Ni-Schiff base complex [Ni 3 (salpen) 2(PhCH 2COO) 2(EtOH)] has been synthesized by combining Ni(ClO 4) 2 · 6H 2O, phenyl acetic acid (C 6H 5CH 2COOH), and the Schiff base ligand, N,N′-bis(salicylidene)-1,3- pentanediamine (H 2salpen). This complex is self-assembled through hydrogen bonding and C-H-π interaction in the solid state to generate a sheet-like architecture, while in organic solvent (CH 2Cl 2), it forms vesicles with a mean diameter of 290 nm and fused vesicles, depending upon the concentration of the solution. These vesicles act as an excellent carrier of dye molecules in CH 2Cl 2. The morphology of the complex has been determined by scanning electron microscopy and transmission electron microscopy experiments, and the encapsulation of dye has been examined by confocal microscopic image and electronic absorption spectra. © 2009 American Chemical Society.