The Nd3+‐doped CaO‐Al2O–B2O3‐CaF2 glasses were prepared by melt‐quenching technique and their optical, spectroscopic, and thermo‐optical properties were studied. The density and refractive index showed an increase with addition of Nd2O3 at the expense of CaO. The electronic polarizability increases with Nd2O3 concentration due to the increase in NBO. The absorption spectra present characteristic bands of Nd3+ transitions from the ground state 4I9/2 to the various excited states. The luminescence spectra show Nd3+ emission at ~880 nm (4F3/2 → 4 I9/2) and ~1064 nm (4F3/2 → 4 I11/2), which increases with Nd2O3 up to 3 wt%. The experimental lifetime decreases when Nd2O3 content increases, mainly due to the nonradiative processes of direct energy transfer between Nd3+ ions (cross relaxation). Results of thermal coefficient of optical path length (dS/dT) for the CaBAl glasses did not present significant changes with Nd2O3 concentration. These with values are comparable to the Fused Silica, and lower than the values measured for the CAS and LSCAS glasses. The results point out this glass system as a good candidate to be used in the development of photonics devices.