Anodic layers have been grown on 304L stainless steel (304L SS) using two kinds of fluoride-free organic electrolytes. The replacement of NH4F for NaAlO2 or Na2SiO3 in the glycerol solution and the influence of the H2O concentration have been examined. The obtained anodic layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and potentiodynamic polarization tests. Here, it was found that, although the anodic layers fabricated within the NaAlO2-electrolyte and high H2O concentrations presented limited adherence to the substrate, the anodizing in the Na2SiO3-electrolyte and low H2O concentrations allowed the growth oxide layers, and even a type of ordered morphology was observed. Furthermore, the electrochemical tests in chloride solution determined low chemical stability and active behavior of oxide layers grown in NaAlO2-electrolyte. In contrast, the corrosion resistance was improved approximately one order of magnitude compared to the non-anodized 304L SS substrate for the anodizing treatment in glycerol, 0.05 M Na2SiO3, and 1.7 vol% H2O at 20 mA/cm2 for 6 min. Thus, this anodizing condition offers insight into the sustainable growth of oxide layers with potential anti-corrosion properties.