New series of copper-salicylaldimine mesogens carrying 4-alkanoyloxy substituents of varied size on the N-phenyl group have been prepared and characterized for their liquid crystalline behaviors. These complexes are commonly smectogenic, and a tilted smectic C phase is enhanced as the alkanoyl group is elongated. Similar tendency has been observed with the ligands, but an orthogonal smectic A phase is not as stable (relative to the smectic C phase) as in the complexes. These behaviors have been interpreted to result from the dipolar interactions as a secondary effect between the carbonyl groups. Their mobility is more restricted in derivatives with longer alkanoyl chains, which would enhance the tilted phase. The relative stability of orthogonal and tilted smectics may be related to the difference in topological arrangement of the polar groups between the complex and its ligand, which have similar smectic layer distances.