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Solution Precursor Plasma Spray (SPPS) is a thermal spraying process that uses a thermal plasma as the heat source and aqueous solutions as the feedstock. SPPS has demonstrated the potential to produce as-deposited coatings comprised of nano-size particles agglomerated into porous spheres with interconnected pores between spheres for SnO2 coatings. These coatings could be advantageous as electrochemical electrodes for gas sensors. This paper discusses the fabrication of as-deposited porous LiFePO4 coatings, of interest as electrodes for battery applications. Different solution chemistries were used to produce a reducing environment for deposition. Solution precursors containing lithium ions, iron ions with phosphoric and phosphorous acids were compared. The microstructures and morphologies of the coatings were examined by SEM and XRD. The results show effects of solution chemistry on the substrate temperature during deposition, and on the phase composition and porosity of the deposit.