Bilayer structures of colloidal PbS quantum dots (QDs) with different sizes are fabricated by two methods: chemical bond anchoring and electrostatic adsorption. Unlike the sample prepared by chemical bond anchoring, we find that the electronic connection between different layers is suppressed in the samples prepared by electrostatic adsorption with charged polyelectrolytes. To clarify the electronic coupling between the QDs and the polyelectrolytes, QDs directly stabilized by charged polyelectrolytes were synthesized. Transmission electron microscopy investigation shows that cross-linked QD networks are formed. Time-resolved photoluminescence measurements indicate that the carrier lifetimes of QDs in networks were greatly reduced. The photoluminescence peak energy increases with a third root of the excitation power. All these observations can be consistently explained considering spatially separated photoexcited carriers in a type-II band alignment. The abnormal behaviors of electrostatic adsorption sample are discussed based on these results. © 2013 World Scientific Publishing Company.