Design and development of cation receptors represent a fascinating area of research, particularly in dealing with chemical and biological applications that require fine-tuning of cation-pi interactions. The electronic nature of a substituent is largely responsible for tuning the strength of cation-pi interaction, and recent studies have shown that substituent resonance effect contributes significantly to such interactions. Using substituent resonance effect as a key electronic factor, we have proposed new cation-pi receptors (1 center dot center dot center dot M+-4 center dot center dot center dot M+; M+ = Li+, Na+, K+, NH4+, and NMe4+). B3LYP/6-311+G(d,p) density functional theory (DFT) calculations show that by using a strategy of resonance donation from six nitrogen atoms via three substituted imidazole subunits, more than 4-fold increase in cation-pi interaction energy (E-M(+)) can be achieved for a single phenyl ring compared to benzene. The E-M(+) = NH4+, NMe4+) of 4 center dot center dot center dot M+, wherein M+ interacts with only one phenyl ring, is significantly higher than E-M(+) a known cation host with several aromatic rings (abstract figure). Our hypothesis on resonance enhancement of cation-pi interaction is verified using several pi-systems (5-10) containing a lone pair bearing six nitrogens and observed that a nitrogen lone pair attached to a double bond is more effective for donation than the lone pair that is directly attached to the benzenoid ring. Further, a convenient strategy to design electron rich pi-systems is provided on the basis of topographical analysis of molecular electrostatic potential.