Multimodal atomic force microscopy (AFM) was used to map charge transfer properties in correlation to the molecular superstructure of poly(ethyldioxythiophene)-poly(styrenesulfonic acid) (see Figure). The lamellar domains of the polymer blend are indicated by phase shifts. Efficient charge injection occurs when lamellar edges of the superstructure are exposed to a conductive AFM probe. Efficiency of charge injection at polymer-electrode interfaces could be enhanced by controlling lamellar orientation.