The hydroboration 1,3- and 1,4-cyclic dienes has been systematically investigated. The behavior of such dienes towards mono and dihydroboration was monitored directly by 11B NMR to identify the actual boron species formed, as opposed to the most common analysis of the resultant oxidation products. Quantitative dihydroboration was achieved for the full range of cyclic dienes investigated including dienes, which were previously reported to be resistant to dihydroboration, leading to the formation of new boron-containing polymeric materials. The conditions favoring dihydroboration are reported as well as full characterisation of the materials. Furthermore, a hydroboration cascade mechanism is proposed for the formation of such boron-containing polymers, supported by both experimental and theoretical data.