We describe the quantitative self-assembly (>90%) of a [4 + 2] octa-imine cage (1) in a CDCl3:CD3CN 9:1 solvent mixture containing 0.5% of acetic acid. Cage 1 is based on two identical aryl-extended calix[4]pyrrole units linked through eight dynamically reversible imine bonds. Cage 1 forms thermodynamically and kinetically highly stable inclusion complexes featuring 1:1 and 2:1 stoichiometry with suitable para-substituted pyridine-N-oxides. The ability of 1 for the pairwise inclusion of two different pyridine-N-oxides led us to investigate its properties as a reactor vessel. The coinclusion of 4-azido pyridine-N-oxide and 4-ethynyl pyridine-N-oxide did not produce a detectable acceleration of their 1,3-dipolar cycloaddition reaction. Conversely, the coinclusion in cage 1 of the same alkyne dipolarophile with 4-azido(alkyl) pyridine-N-oxides (alkyl= methyl, ethyl) produced significant reaction acceleration. We quantified the reactions’ acceleration with an effective molarity (EM) of ∼103 M, corresponding to the more prominent reported value of a bimolecular 1,3-dipolar cycloaddition reaction in a molecular vessel by directly detecting the ternary Michaelis complex. The included reactions are quantitative and regioselective, yielding exclusively the 1,4-disubstituted triazole isomers. We propose that the selectivity of 1 in accelerating the included 1,3-dipolar cycloadditions is related to (a) the entropy gain provoked by the reaction’s inclusion, (b) the rigidity of the container, and (c) the spatial fixation of the polar knobs (pyridine-N-oxide) carrying the reacting groups in its two functionalized hemispheres. The two latter characteristics render the distance between the reacting groups (azido and ethynyl) almost fixed by design, thus allowing or not achieving the transition state’s geometry. We support our hypothesis with the help of DFT calculations of the inclusion complexes’ structures.