Sufficient spatial separation of photo-generated electrons and holes plays a significant role in affecting the efficiency for solar energy conversion. Non-equivalent facets of a catalyst are known to possess different charge distribution properties. Here, we report that hexagonal 6H-SiC, a metal-free, environmentally friendly, polar semiconductor, exhibits different charge distribution and photocatalytic properties on naturally occurring Si-{0001} and {10-10} facets. Very strong selectivity of metals in situ photodeposition occurs in these two facets, demonstrating that the photo-excited electrons are assembled only on polar Si-{0001} facets while the holes are assembled on non-polar {10-10} facets. Consequently, reduction reactions occur only on the Si-{0001} facets with noble metals, and meantime oxidation occurs only in {10-10} with metal oxide. We show that the activity of photocatalytic water splitting is significantly enhanced by this kind of selective depositions resulting from the charge spatial separation. The underlying mechanism is investigated in terms of experimental evidence and first principles calculations. Our results demonstrate that the utilization of facets with opposite catalytic characteristics could be a feasible means to enhance the photocatalytic performance in diverse semiconducting materials. This is, in particular, of interest for polar semiconductors, as their particles always naturally occur in both polar facets and non-polar ones without needing facet engineering.