Five novel lanthanide (Tb3+, Eu3+, Gd3+, Sm3+ and Dy3+ ) complexes with dicyandiamide in 2- ethoxyethanol were synthesized and characterized. The spectroscopic studies indicate the formation of lanthanide complexes. The thermal analysis data indicate a series of wt. loss of the ligand at different temperatures. The photophysical properties of these complexes were studied using ultraviolet-visible absorption spectra, fluorescence excitation and emission, and phosphorescence spectra. The ligand acts as the main energy donor and luminescence sensitizer of the Ln3+ ions. The luminescence intensities of Tb3+complex show the strongest luminescence and Sm3+ species show the weakest emission. Life-time studies on (Tb3+ and Eu3+) complexes indicate biexponential nature of the luminescence decay.