The work in this investigation deals with the syntheses, characterization, crystal structures and catechol oxidase activity of four diphenoxo-bridged Comte compounds of composition [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 6H(2)O (1), [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O (2), [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 3.5H(2)O (3) and [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 2.5H(2)O(N-3)(4)]center dot CH3CN"2.5H20 (4), and two diphenoxo-bridged ColliColl compounds of composition [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 2H(2)O) (5) and ((CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot H2O (6). In these compounds, H2LMe-pn, H2LEt-pn, H2LMe-Me2pn and H-2(LEt-Me2Pn) are four Robson type tetraiminodiphenolate macrocyclic ligands, in which the superscript Me and Et indicate that the dialdehyde components are 4-methyl-2,6-diformylphenol and 4-ethyl-2,6-diformyl-phenol, respectively, white pn and Me2pn indicate that the diamine components are 1,3-diaminopropane and 2,2-dimethyl-1,3-diaminopropane, respectively. The Contour compounds 1-4 are further characterized by 1H NMR spectra. Compounds 1 and 3 are prepared following a metal-templated synthesis, while compounds 2 and 4 are prepared by direct synthesis, which includes using a pre-isolated macrocycle, [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O, as a reactant. On changing the diamine component of the corresponding macrocycie from 1,3-diaminopropane to 2,2-dimethyl-1,3diaminopropane, but otherwise following the similar reaction procedure (both direct and template), the ColliColl compounds [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O (5), [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O (6), [(CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O) (CoCoLMe-Pn)-Co-III-L-III-(N-3)(4)]center dot 4H(2)O (5A; lnorg. Chim. Acta, 2014, 412, 38) and [COIIIC011 LEt-Me2pn( IN) 3 I.MeCN (6A; Dalton Trans., 2013, 42, 4561) are formed, rather than Canton' compounds. Like compounds 5A and 6A, all the compounds 1-6 show catechol oxidase activity (substrate: 3,5-di-tert-butyl catechot). The kinetic parameters for 1, 3 and 6 have been determined. Their Kcat values are, respectively, 212.6, 188.0 and 191.3 h-1. ESI-MS (positive) spectra of some representative cases (with and without the substrate) have been recorded and the positive species have been assigned well. Unprecedented and surprising aspects of the composition/structure and properties of the complexes in this investigation have been discussed.