Abstract In this work, the Calibration-Free approach for Laser-Induced Breakdown Spectroscopy (CF-LIBS) was applied for the first time to radially resolved spectra emitted by a laser-induced plasma. The radial profiles of plasma temperature and electron number density were used to calculate the local relative concentration of the elements of interest. We analyzed a set of profiles of the local spectral emission coefficient obtained previously by means of spatial deconvolution of the spectra from a copper-based alloy (Cu 93, Fe 5, Mn 1, Ni 1 wt.%) laser-induced plasma. A spatially integrated spectrum of the same plasma was also analyzed for comparison purpose. The relative abundance of the minor components Fe, Mn and Ni was calculated. The results obtained from the central region of the plasma were closer to the nominal concentrations than those obtained from the spatially integrated spectrum. However, an increasing deviation was observed towards the plasma edge. It is proposed that this deviation could be the result of a gradual departure from Local Thermodynamic Equilibrium (LTE) conditions due the significant decrease of the electron density at the external shells of the plasma.