This manuscript deals with a complex analysis of acoustic emission signals that were recorded during freeze-thaw cycles in test specimens produced from air-entrained concrete. An assessment of the resistance of concrete to the effects of freezing and thawing was conducted on the basis of a signal analysis. Since the experiment simulated testing of concrete in a structure, a concrete block with the height of 2.4 m and width of 1.8 m was produced to represent a real structure. When the age of the concrete was two months, samples were obtained from the block by core drilling and were subsequently used to produce test specimens. Testing of freeze-thaw resistance of concrete employed both destructive and non-destructive methods including the measurement of acoustic emission, which took place directly during the freeze-thaw cycles. The recorded acoustic emission signals were then meticulously analysed. The aim of the conducted experiments was to verify whether measurement using the acoustic emission method during Freeze-thaw (F-T) cycles are more sensitive to the degree of damage of concrete than the more commonly employed construction testing methods. The results clearly demonstrate that the acoustic emission method can reveal changes (e.g., minor cracks) in the internal structure of concrete, unlike other commonly used methods. The analysis of the acoustic emission signals using a fast Fourier transform revealed a significant shift of the dominant frequency towards lower values when the concrete was subjected to freeze-thaw cycling.