Alkali-Silica Reaction (ASR), which develops over time into a harmful internal reaction in concrete, produces a harmful gel due to the reaction between the reactive silica in the aggregate and the alkalis of the pore solution. Due to the multi-scale nature of this long-term phenomenon, understanding its mechanism in concrete structures remains difficult to assess. Accelerated Mortar Bar Testing (AMBT) ASTM C1260 is among the commonly used methods to understand ASR formation in a short time. In this study, the chemical characterisation of concretes produced from volcanic rock type basalt aggregate was compared with the chemical characterisation of ASR concretes after AMBT was applied. In addition, 20% FA was substituted into the concrete to investigate the effect of fly ash (FA) on ASR. Specimens with limestone aggregate (PL), basalt aggregate (BBC) and 20% basalt aggregate with fly ash substitution instead of cement (BBC20FA) were prepared for the investigation. Scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques were used to characterise the morphology and analytical composition of the concretes. It was determined that basalt aggregate does not cause ASR and its use with fly ash increases the strength and durability of concrete.