In this study, dilatometry and metallography were used to investigate the effect of silicon and copper alloying on the decomposition kinetics of 54SiCr6 steel during continuous slow cooling. It is different from the published literature for using the approach of the local activation energy of the austenite decompositionEfand the local Avrami exponentnof the volume fraction of the transformed phasefto study the kinetics of austenite-pearlitic transformation in cooled 54SiCr steel at slow cooling rates. The Johnson–Mehl–Avrami equation was used to determine the dependence of the local activation energy for austenite decompositionEfand the local Avrami exponentnon the volume fraction of the transformed phasef. The mechanism of the austenite decomposition was analysed based on the calculated values ofn. Both the local and average activation energies were used to evaluate the alloying effect, and the results were compared with those obtained from other methods. The type of microstructure formed as a result of cooling at rates of 0.5 K/s, 0.3 K/s, 0.1 K/s and 0.05 K/s was determined. The effects of changes in the cooling rate and the content of silicon (1.5–2.5 wt.%) and copper (0.12–1.47 wt.%) on the dimension of nucleation and growth kinetics of the transformed phase were studied. It was revealed that the pearlite microstructure was formed predominantly in 54SiCr6 steel as a result of continuous cooling at slow cooling rates. It was also found that alloying this steel with copper led to a significant decrease in the value ofEf,as well as to a change in the mechanism of the kinetics of the austenite-pearlite transformation, which was realised in predominantly two- and three-dimensional nucleation and growth at a constant nucleation rate. At the same time, alloying this steel with silicon led only to a slight change inEf. The results of the study of 54SiCr steel presented the dependence of the activation energy of transformation and the local Avrami exponent on the volume fraction of the transformed phase at a given cooling rate at different copper and silicon contents. In addition, the study provides insight into the mechanism of kinetics in cooled 54SiCr steel as a function of the cooling rate.