Black phosphorus (BP), a promising 2D material for electronics, energy storage, catalysis, and sensing, has sparked a research boom. However, exfoliated thin-layered BP is unstable and can easily be degraded under environmental conditions, severely limiting its practical applications. In this context, a simple and cost-effective method has been proposed that involves electrochemically exfoliating BP and simultaneously electrochemically depositing aluminum oxide (AlO x ) for passivation of the exfoliated BP. The ambient stability of the exfoliated BP is studied using a time-dependent atomic force microscope (AFM). The AlO x capping layer significantly improves the environmental stability of BP compared to uncapped BP. The thermal stability of the resulting BP is evaluated using power-dependent Raman spectroscopy. The results show that the AlO x -passivated BP has increased thermal stability, with only a slight shift in peak position toward higher Raman power intensity. These properties can make the material suitable for stable energy storage devices. Interestingly, the electrochemical exfoliation and passivation processes resulted in the BP with a twist angle (9.86°), which is expected to exhibit unique electronic properties similar to those of graphene with a twist angle.