This article begins by describing the synthesis and recognition properties of the cucurbit[n]uril homologues CB, CB, CB, CB, and CB. Subsequently, we describe the state-of-the-art in understanding the mechanism of CB[n] formation. We describe the experiments that establish that glycoluril (1 H) undergoes condensation with formaldehyde by a combination of chain-growth and step-growth polymerization processes. Chain-growth processes deliver methylene bridged glycoluril oligomers 2 C–8 C as intermediates that may undergo macrocyclization to nor-seco-CB[n] when the oligomer is long enough (5 C–8 C) and subsequently form CB[n]. Step-growth processes allow oligomers to condense to give longer oligomers connected by a single CH2-bridge that undergo macrocyclization to deliver (±)-bis-nor-seco-CB and bis-nor-seco-CB. Lastly, we describe some of the exciting new recognition processes of the newly formed members of the CB[n] family. For example, bis-nor-seco-CB undergoes homotropic allostery during ternary complex formation, (±)-bis-nor-seco-CB exhibits moderately diastereoselective recognition processes (d.r. up to 88 : 12) with chiral ammonium ions in water, and nor-seco-CB functions as an aldehyde reactive CB[n] synthon that can control the folding of alkanediammonium ions into a backfolded conformation in water.