Derivatized cucurbiturils can be efficiently prepared and utilized for forming cucurbituril assemblies. These cucurbituril assemblies, in turn, can form affinity binding pairs with polyamines structures that are designed capable of binding to these assemblies. The resulting affinity pairs are highly advantageous over the presently known affinity pairs and therefore can be efficiently utilized in a myriad of application. Thus, according to one aspect of the present invention there is provided a cucurbituril comprising at least one functional group covalently attached hereto, whereby the at least one functional group being for forming an assembly of at least two cucurbiturils. According to further features in preferred embodiments of the invention described below, the cucurbituril is selected from the group consisting of CB[5], CB[6], CB[7], CB[8] and CB[n], wherein n is an integer that equals to or is lower than 20. Preferably the cucurbituril is selected from the group consisting of CB[5], CB[6], CB[7] and CB[8]. According to still further features in the described preferred embodiments the assembly is selected from the group consisting of a dimer, a trimer, a polymer, an oligomer, a dendrimer and a cluster of the cucurbituril.