Several frontiers in photon-atom interaction require the development of inexpensive fine-scale and structurally complex periodic materials. For example, the crystal structure and shape/complexity of photonic crystal bases greatly influences the capability of the materials to exhibit superior electro-optic properties. The potential to alter the dynamics of spontaneous emission processes has implications for the enhancement of photocatalytic reactions, which play an important role in environmental remediation strategies, as well as for more efficient photovoltaic and solar cell devices. Here, we study self-assembly of non-spherical mushroom-cap shaped colloids into ordered photonic crystal structures, aided by fluorescent nanoparticle depletants. Core-shell nanoparticles (~30 nm in diameter) consisting of the organic fluorophore tetramethylrhodamine isothiocyanate (TRITC) encapsulated in a silica shell were co-assembled with polystyrene non-spherical particles using a convective approach. Colloidal phases were determined as a function of the concentration ratio of nanoparticles to non-spherical colloids. The modification of dye emission characteristics due to changes in the local density of photon states was explored in the reduced symmetry photonic crystal system (based on mushroom-cap basis) and compared with similar effects in a simple sphere based photonic crystal.