The recombination of intrinsic point defects in dislocation-free silicon single crystals is investigated. It is established experimentally and confirmed by thermodynamic calculations that this process in the vicinity of the crystallization front is hindered by the recombination barrier. The recombination parameters (such as the recombination barrier height, the recombination time, and the recombination factor) for the model describing the dynamics of point defects at low and high temperatures are evaluated in terms of the heterogeneous mechanism of nucleation and transformation of grown-in microdefects. It is confirmed that the decomposition of a supersaturated solid solution of point defects can occur according to two mechanisms, namely, the vacancy and interstitial mechanisms. Vacancies and intrinsic interstitial silicon atoms find sinks in the form of oxygen and carbon background impurities. It is demonstrated that the formation of “intrinsic point defect – impurity” pairs is a dominant process in the vicinity of the melting temperature.