In this work we try to synthesize MoO3 and WO3 nanoceramics by understanding the effects of precursor parameters on the electrospinning process. We synthesized polymer based composites with molybdenum oxide and Tungsten oxide under straight polarity i.e. keeping needle charged and collector grounded; as well as reverse polarity i.e. keeping the needle grounded and collector charged. We observed MoO3 nanotubes after heat treatment of the composite mats spun in reverse polarity. The reason for formation of nanotubes is the presensce of molybdenum oxide particles as an outer shell surrounding the polymer fiber core in the spun mats, this core shell configuration can be correlated with the zeta potential of the sol gel that is electronegative; and thus the sol forms a shell around the polymer when the collector is positively charged. For WO3, we obtained a nanogrid structure after thermal treatment under both conditions (straight and reverse polarity). The reason for the formation of the grids is due to the immiscibility of the metal oxide particles in colloid solution. The nanostructures obtained for MoO3 and WO3 are very promising candidates to be used as solar cells, photocatalysts or as negative electrodes in Li-ion batteries.