Recent demonstration in augmenting the efficiency of aqueous Rhodamine dye lasers using cucurbit[7]uril (CB[7]), a deaggregating and photostabilizing host, has drawn interest in the synthesis and characterization of spectroscopic grade CB[7] in larger quantities. Synthesis of cucurbituril group of macrocycles always leads to the formation of various homologues of CB[n]s (n=5–7) with CB[7] as the minor product. The literature procedure has been optimized to get pure CB[7] in 12–14% yield by fractional crystallization and the purity was checked by NMR, MS and spectrophotometric titration. Laser performances of the synthesized and commercial CB[7] sample as an additive were evaluated using Nd-YAG (532 nm) pumped Rhodamine B aqueous dye lasers and comparable results were obtained.