Controlling supramolecular self-assembly is a fundamental step towards molecular nanofabrication, which involves a formidable reverse engineering problem. It is known that a variety of structures are efficiently obtained by assembling appropriate organic molecules and transition metal atoms on well-defined substrates. Here we show that alkali atoms bring in new functionalities compared with transition metal atoms because of the interplay of local chemical bonding and long-range forces. using atomic-resolution microscopy and theoretical modelling, we investigate the assembly of alkali (Cs) and transition metals (mn) co-adsorbed with 7,7,8,8-tetracyanoquinodimethane (TCnQ) molecules, forming chiral superstructures on Ag(100). Whereas mn-TCnQ 4 domains are achiral, Cs-TCnQ 4 forms chiral islands. The specific behaviour is traced back to the different nature of the Cs-and mn-TCnQ bonding, opening a novel route for the chiral design of supramolecular architectures. moreover, alkali atoms provide a means to modify the adlayer electrostatic properties, which is important for the design of metal-organic interfaces.