Herein, a study of the plasma electrolytic oxidation (PEO) of niobium in an anodising bath composed of potassium silicate (K2SiO3) and potassium hydroxide (KOH) is reported. The effects of the K2SiO3 concentration in the bath and the process voltage on the characteristics of the obtained oxide layers were assessed. Compact, barrier-type oxide layers were obtained when the process voltage did not exceed the breakdown potential of the oxide layer. When this threshold was breached, the morphology of the oxide layer changed markedly, which is typical of PEO. A significant amount of silicon, in the form of amorphous silica, was incorporated into the oxide coatings under these conditions compared with the amount obtained with conventional anodising. This surface modification technique led to an improvement in the corrosion resistance of niobium in Ringer’s solution, regardless of the imposed process conditions.