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Silver nanowires (AgNWs) represent an excellent material for many advanced applications due to their thermal and electrical properties. However, synthesising materials with the desired characteristics requires knowledge of the parameters affecting their size and an appropriate fabrication method. This paper presents a study on the synthesis of silver nanowires using the polyol process by conventional and microwave heating. Various polyols (1,2-ethanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol) with different viscosities and dielectric properties were used as reductants. It resulted in nanowires with an average diameter of 119–198 nm. It was found that, in contrast to the viscosity and dielectric constant of the alcohol used, the heating method had a limited effect on the average diameter and length value of the final product. The performed studies indicate an optimal strategy for fabricating one-dimensional silver nanostructures using the polyol method.