A new family of homochiral lanthanide dinuclear complexes based on a chiral carboxylate, namely [Ln(R-pba)3(phen)]2 (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9) and Ho (10), R-pba = (R)-2-phenylbutyric acid, phen = 1,10-phenanthroline), have been synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Complexes 1–10 are isostructural and crystallize in the chiral space group P21. Their optical activity and enantiomeric nature were confirmed by the circular dichroism spectra. Complexes 6, 8 and 9 exhibit strong fluorescent emissions with typical narrow emission bands of lanthanide ions and 6 and 8 display relatively high quantum yields. Magnetic investigations revealed that the weak antiferromagnetic exchange and/or the depopulation of the Ln(III) excited Stark sub-levels exist in 7–10.