Understanding charge collection and trapping mechanisms is crucial for using hexagonal boron nitride (h-BN) as active layers for many photonic and electronic devices such as deep UV detectors and emitters, neutron detectors, and single photon emitters. Charge collection and trapping mechanisms in h-BN epilayers have been investigated by probing impurity related optical emissions under an applied electrical field. Our results suggested that the existence of oxygen impurities affects the charge collection efficiency and results in an additional emission peak at 3.75 eV, corresponding to a donor-acceptor pair (DAP) recombination involving ON (oxygen residing on the nitrogen site) donors and the VB-H (boron vacancy bonded with hydrogen complex) deep level acceptors. Experimental results further revealed that the applied electric field induces an anti-correlation between the emission intensity of the DAP transition and the charge collection efficiency from which it was shown that it is possible to find an expression to quantitatively measure the maximum charge collection efficiency in h-BN. The results introduce not only a coherent picture for the relationship between common impurities in h-BN and charge collection and trapping mechanisms but also useful insights into possible approaches to improve the quality, purity, and charge collection of the h-BN epilayers.