In this study we focus on the coordination chemistry of a family of three flexible benzotriazole-based ligands (L1-L3) using Cobalt(II) salts. Our efforts have resulted to the formation of ten novel compounds, formulated as [Co2(L1)2Cl4]·2MeCN (1·2MeCN), Co2(L1)2Br4 (2), [Co(L2)Cl2]·MeCN (3·MeCN), Co(L2)Cl2 (4), [Co2(L2)2Br4]·2MeCN (5·2MeCN), [Co(L2)2(NO3)2]·2MeCN (6·2MeCN), [Co2(L3)2Cl4]·2MeCN (7·2MeCN), Co2(L3)2Cl4 (8), Co2(L3)2Br4 (9), and Co(L3)2(NO3)2 (10). The structures have been well characterised through X-Ray crystallography, FT-IR, ESI-MS, PXRD, Elemental Analysis and TGA studies. The compounds show a large structural variety depending on synthetic parameters (ratio, temperature and metal salt) and the ligand selection (various conformations in each ligand). When tuned appropriately, these factors drastically affect dimensionality, metal geometry and the nuclearity of the final product, resulting in a range of 0D dimers (1, 3, 5, 8, 9), 1D (2, 7, 10) and 2D (4, 6) coordination polymers (CPs). A temperature-induced single-crystal to single-crystal transformation of compound 3 to 4 is additionally reported. The magnetic properties of representative compounds (4, 7, 9) are subject to large changes with only minor structural variations, suggesting that tetrahedral Co(II) nodes in CPs or MOFs could function as sensitive reporters of small changes in the local environment.