The paper analyses the possibility of post weld heat treatment (PWHT) quality assessment with the help of magnetoacoustic emission (MAE) signal measurements. Two welded superheater tubes, made of high chromium VM12 steel, were analysed—as welded and heat treated one. The analysed sample in the as welded state exhibited significantly higher hardness, accompanied by a big difference in the MAE signal intensity (of order of about 50%). In order to explain that, the influence of tempering on the MAE signal intensity is demonstrated for the very similar X20CrMoV12.1 steel. It is shown that the observed increase of the MAE intensity as a function of annealing time is directly correlated with the change in hardness. The as described dependence allows to propose a method based on the MAE signal measurements as a new tool for the PWHT assessment.