The paper is devoted to detailed surface studies of the Fe82Al18 alloy prepared from high purity Fe and Al by arc melting. The results summarize observations of the surface sensitive methods – high resolution scanning electron microscopy (HRSEM), slow energy electron microscopy (SLEEM), magneto-optical Kerr effect (MOKE), and conversion electron Mössbauer spectrometry (CEMS). Morphology of grains and grain boundaries obtained by HRSEM is observed in more detail by SLEEM. The CEMS results analyzed using free components with characteristic hyperfine parameters and by theoretical model, give evidence for A2 order of the as-prepared and as-quenched Fe82Al18 sample surfaces. A small contribution of the oxide layer influences the shape of hysteresis loops and domain structure of the sample surface above all in the as-quenched state.