Display omitted •Six Colombian asphaltenes bearing high compositional variability were studied.•Compositional/structural parameters were introduced based on different techniques (FT-ICR MS, MS2, TGA-MS, FT-IR, 1H/13C NMR).•DBE26/DBE15 ratio by tandem mass spectrometry provided the archipelago/island structural prevalence in asphaltenes samples.•The predominancy of peri-condensed and cata-condensed structures as an additional asphaltenes’ structural characteristic were disclosed. The advanced characterization of asphaltenes has been extensive and fruitful during the last two decades but with many gaps. Despite the efforts to reveal the molecular architectures that dominate asphaltenes, some pieces of the puzzle are still missing. Critical information that can lead to a global picture of asphaltenes remains scarce. The last in-depth discussions have been around the island/archipelago architectures found in the asphaltenes from the Wyoming deposit and Athabasca bitumen, respectively. With the premise of stablishing an island and archipelago motif domain, along this contribution we extend the discussion throughout six diverse Colombian asphaltenes from different origins. We set a parameterization based on outer island/archipelago structures and experimental data obtained from different characterization techniques such as elemental analysis, 1H NMR, 13C NMR, IR spectroscopy, FT-ICR-MS, tandem MS, and TGA for thermal combustion and pyrolytic/coke formation. In each case, compositional parameters were proposed to classify asphaltenes as islands o archipelago dominant, with cata- or peri-condensed aromatic systems. Particularly, by using tandem mass spectrometry data, a new parameter named island factor FIsland was proposed to establish the island/archipelago prevalence of asphaltenes. The advantage of this broad analysis leads us to conclude that there is not only a marked difference between archipelagos and islands but also the type of conjugated system cata- or peri-condensed, which makes visible the relevance of having a broad concept of the asphaltene molecular architecture and their impact on large-scale properties. This report consists of a comprehensive discussion using experimental techniques applied on diverse asphaltenes not reported in the literature before.