In the present work, electrospraying of an organic molecule is carried out using various solvents, obtaining fibril structures along with a range of distinct morphologies. Solvent characteristics play a major role in achieving the morphology of the organic material. A thiophene derivative (7, 9-di (thiophen-2-yl)-8H-cyclopenta[a]acenaphthylen-8-one) (DTCPA) of donor-acceptordonor (DAD) architecture is used to study this solvent effect. Seven solvents with decreasing vapour pressure are selected for experiments. Electrospraying is conducted at a solution concentration of 1.5 wt % and a constant applied voltage of 15 kV. Gradual transformation in morphology of the electrospun product from spikes-sphere to only spikes is observed. A mechanism describing this transformation is proposed based on the electron micrograph analysis and XRD analysis. These data indicate that the morphological change is due to the synergistic effect of both vapour pressure and dielectric constant of the solvents. Through a reasonable control over the crystallites size and morphology along with supporting transformation mechanism theory, this study elucidates electrospraying as a prospective method for designing the architectures in organic electronics.