For an observer hovering [I say hover because by definition there are no orbits for an observer at the photon sphere] at the photon sphere for a non-maximal de Sitter-Schwarzschild black hole, a simple accelerometer will tell an observer which horizon is which. The reason for this is that in order to hover at the photon sphere the observer must take up a non-inertial local frame with a directional bias decided by the direction of the BH event horizon. 

In the maximal de Sitter-Schwarzschild spacetime the BH singularity disappears and the observer will not be able to tell the difference between the two horizons as there is an automorphism of that spacetime which will map one horizon to the other.