A new technique is presented in this paper for the analysis of welding process emission spectra to accurately estimate in real-time the plasma electronic temperature. The estimation of the electronic temperature of the plasma, through the analysis of the emission lines from multiple atomic species, may be used to monitor possible perturbations during the welding process. Unlike traditional techniques, which usually involve peak fitting to Voigt functions using the Levenberg–Marquardt recursive method, sub-pixel algorithms are used to more accurately estimate the central wavelength of the peaks. Three different sub-pixel algorithms will be analysed and compared, and it will be shown that the LPO (linear phase operator) sub-pixel algorithm is a better solution within the proposed system. Experimental tests during TIG-welding using a fibre optic to capture the arc light, together with a low cost CCD-based spectrometer, show that some typical defects associated with perturbations in the electron temperature can be easily detected and identified with this technique. A typical processing time for multiple peak analysis is less than 20 ms running on a conventional PC.