Here, we report (i) a synthetic strategy for the structural control at the molecular level for a series of periodic co-polymers, namely bipyridine-containing covalent triazine frameworks (CTFs), (ii) a general protocol for the consistent measurement of their resulting electronic properties, e.g. frontier orbital position allignement, a feat not described yet, and (iii) their correlation with the obtained catalytic performances in photochemical hydrogen evolution reaction (HER) which reaches 7.2 mmol/h/g cat .