Hematite (α-Fe2O3) nanoparticles were diffused of two different shapes (spherical and cubical) in PEDOT:PSS matrices below the percolation threshold. Increases in conductivity within a distinct range in concentration were observed in the dark and under simulated solar illumination. The effect was ascribed to a generalized Poole-Frenkel effect in conjunction with basic properties of heterojunctions and electrostatic dipoles, and verified through data fitting. A difference in behaviour between sphere- and cube-based nanocomposites was also observed.