The solar-power conversion efficiencies of colloidal quantum dot solar cells have advanced from sub-1% reported in 2005 to a record value of 8.5% in 2013. Much focus has deservedly been placed on densifying, passivating and crosslinking the colloidal quantum dot solid. Here we review progress in improving charge extraction, achieved by engineering the composition and structure of the electrode materials that contact the colloidal quantum dot film. New classes of structured electrodes have been developed and integrated to form bulk heterojunction devices that enhance photocharge extraction. Control over band offsets, doping and interfacial trap state densities have been essential for achieving improved electrical communication with colloidal quantum dot solids. Quantum junction devices that not only tune the optical absorption spectrum, but also provide inherently matched bands across the interface between p- and n-materials, have proven that charge separation can occur efficiently across an all-quantum-tuned rectifying junction.