We report a topotactic reaction strategy to achieve the oriented attachment (OA) of colloidal metal chalcogenide quantum dots into micrometer-sized nanosheets and nanobelts (up to 6-7 μm) on both mechanically rigid and flexible substrates. The nonstoichiometric composition, crystallization and Ag doping were controlled. The strong surface adsorption of cations and thiol ligands facilitated micrometer-scale three-dimensional OA. The cations induced the formation of electrostatic forces, cation passivation on the nanosheet surface and overlap packing of the nanosheets, enabling good contact with the substrates and improved electron transport without severe obstruction of organic insulating barriers. The observation of weak anti-localization phenomena and Hall effect sensitivity (up to 188%) of non-stoichiometric Ag 2-δ Te nanosheet films as well as the improved I-V and photoresponse properties of Ag-doped CdX nanosheet films confirm efficient electron transport. The stable I-V properties of these nanosheet films on flexible substrates, even under bending forces, testify to their potential in flexible device applications.