Microstructure evolutions of thermosetting resin coating layers fabricated by electrostatic spray deposition (ESD) at various processing conditions were investigated. Two different typical polymer systems, a thermosetting phenol-formaldehyde resin and a thermoplastic polyvinylpyrrolidone (PVP), were employed for a comparative study. Precursor solutions of the phenol-formaldehyde resin and of the PVP were electro-sprayed on heated silicon substrates. Fundamental differences in the thermomechanical properties of the polymers resulted in distinct ways of microstructure evolution of the electro-sprayed polymer films. For the thermosetting polymer, phenol-formaldehyde resin, vertically aligned micro-rod structures developed when it was deposited by ESD under controlled processing conditions. Through extensive microstructure and thermal analyses, it was found that the vertically aligned micro-rod structures of phenol-formaldehyde resin were formed as a result of the rheological behavior of the thermosetting phenol-formaldehyde resin and the preferential landing phenomenon of the ESD method.