The reaction mechanism of the cycloaddition of 10 1,3-dipoles with the two dipolarphiles ethene and acetylene is investigated and compared using the Unified Reaction Valley Approach in a new form, which is based on a dual-level strategy, an accurate description of the reaction valley far out into the van der Waals region, and a comparative analysis of the electronic properties of the reaction complex. A detailed one-to-one comparison of 20 different 1,3-dipolar cycloadditions is performed, and unknown mechanistic features are revealed. There are significant differences in the reaction mechanisms for the two dipolarophiles that result from the van der Waals complex formation in the entrance channel of the cycloadditions. Hydrogen bonding between the 1,3-dipoles and acetylene is generally stronger, which leads to higher reaction barriers in the acetylene case, but which also facilitates to overcome the problem of a reduced charge transfer from 1,3-dipole to acetylene. Mechanistic differences are found in the prechemical and chemical reaction regions with regard to reactant orientation, preparation for the reaction, charge transfer, charge polarization, rehybridization, and bond formation. It is shown that similarities in the reaction barriers as determined by CCSD(T)-F12/aug-cc-pVTZ calculations result from a fortuitous cancellation of different electronic effects. In general, a caveat must be made with regard to oversimplified descriptions of the reaction mechanism based on orbital theory or energy decomposition schemes.