An analysis of the nucleation mechanism of pyramids formed in (100) silicon in Na2CO3/NaHCO3 solution has been carried out. This texturization process of silicon by means of Na2CO3/NaHCO3 solutions is of special interest because it can be applied to the silicon solar cell industry to texture solar cell surfaces to decrease the front reflection and enhance light trapping in the cells. For this purpose, two microscopy techniques—scanning electron microscopy and atomic force microscopy—have been used to study the different stages of pyramidal nucleation and formation. The different aspects and factors involved in the texturization process require different analysis conditions and microscopy resolution. Tracing the transformation of determined surface areas and structures has been achieved, contributing clarification of the mechanism of pyramid nucleation in Na2CO3/NaHCO3 solutions.