K4Nb6O17 is a layered semiconductor possessing two different layer structures, i.e., interlayers I and II. The present paper reports on the selective synthesis of two types of layered niobate hybrid materials by the introduction of 5,10,15,20-tetrakis(1-methyl-4-pyridinium)-21H,23H-porphyrin (TMPyP4+) into either interlayer I or into both I and II by a guest-guest exchange method using the intercalation compounds (MV2+)(x)K4-2xNb6O17 and (PrNH3+)(x)H4-xNb6O17 as precursors.