Reductive catalysis with earth-abundant metals is currently of increasing importance and shows potential in replacing precious metal catalysis. In this work, we revealed catalytic hydroboration and hydrosilylation of ketones and aldehydes achieved by a structurally defined manganese(II) coordination polymer (CP) as a precatalyst under mild conditions. The manganese-catalysed methodology can be applied to a range of functionalized aldehydes and ketones with turnover numbers (TON) of up to 990. Preliminary results on the regioselective catalytic hydrofunctionalization of styrenes by the Mn-CP catalyst are also presented.