The wet-chemical treatment of silicon wafers is an important production step in photovoltaic and semiconductor industries. Solutions containing hydrofluoric acid, ammonium peroxodisulfate, and hydrochloric acid were investigated as novel acidic, NOx-free etching mixtures for texturization and polishing of monocrystalline silicon wafers. Etching rates as well as generated surface morphologies and properties are discussed in terms of the composition of the etching mixture. The solutions were analyzed with Raman and UV/vis spectroscopy as well as ion chromatography (IC). The silicon surfaces were investigated by scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), diffuse reflection infrared spectroscopy (DRIFT), and X-ray photoelectron spectroscopy (XPS). Surprisingly, pyramidal surface structures were found after etching SiC-slurry as well as diamond wire-sawn monocrystalline Si(100) wafers with hydrochloric acid-rich HF-(NH4)2S2O8-HCl mixtures. Acidic etching solutions are generally not known for anisotropic etching. Thus, the HNO3-free mixtures might allow to replace KOH/i-propanol and similar alkaline solutions for texturization of monosilicon wafers at room temperature with less surface contamination. Besides, common HNO3-based etching mixtures may be replaced by the nitrate-free system, leading to significant economic and ecological advantages.