A dissatisfied THRUSH collaborator tips U.N.C.L.E. off to a new deadly hiccup gas. A pendant he wears leads Illya to Greenwich Village and an art gallery run by Mark Ole, a THRUSH agent. Starving artist Sylvia Harrison joins Illya, who is nearly suffocated at the hands of a foam producing machine.

Solo and Illya protect Miranda Bryant, the wife of a presidential candidate, from a THRUSH plot to kidnap her, not realizing that she has already been kidnapped and replaced with a double Irina, an unwitting dupe of THRUSH. When they do catch on, the candidate, Senator Bryant and his aide Fairbanks, agree to play along but Fairbanks is the one behind the plot to put a THRUSH agent in the White House.

In Rome, American tourist Darlene Sims becomes the unwitting carrier of a perfume atomizer with a secret formula. THRUSH uses a suave ladies man Cesare Guardia to charm Darlene, but he falls in love with her in the process.