Complexes of t-butyl alcohol with norbornene and its monocyclic constituents cyclopentene and cyclohexene are studied via their OH stretching fundamental transitions in supersonic jet expansions. Compared to OH....OH hydrogen bonds, the spectral shifts due to OH.....pi bonding in the mixed dimers are reduced by a factor of 2. Mixed trimers show substantially different spectral signatures due to cooperative effects. Regioselective docking on the two sides of the double bond in norbornene is observed. Harmonic modeling of the spectra using dispersion-corrected hybrid functionals is quite successful, suggesting a high predictive power for this poorly explored class of complexes between alcohols and alkenes.