This paper reports the effects of organic binders on the crystal microstructure of unsupported, Pd2+-impregnated TiO2 membranes. The organic binders used in this study were polyvinyl alcohol and hydroxypropyl cellulose. The use of the binders is important in the production of crack-free membranes. However, the use of the binders influenced the microstructure of the unsupported TiO2 membranes. X-ray diffraction analysis utilized showed that the addition of binders has caused aggregation of palladium oxide (PdO) during its formation in the TiO2 network. This phenomenon directly affects the effectiveness of PdO presence in the suppression of anatase-rutile phase transition. N-2 adsorb/desorption analysis was conducted to investigate the Pd2+-TiO2 membrane morphology at different Pd2+ loading. Based on the observation, the presence of 2 wt% Pd2+ in the TiO2 microstructure has significant impacts on the increment of surface area, pore volume, and average pore width from the original TiO2. However, the surface area shows decrement after the Pd2+ loading was further increased from 2 to 6 and 10 wt%.