ZnO nanorods and Mn/ZnO microflowers with nano-sized petals exhibit singly ionized oxygen vacancies, V+O. This is strongly supported by a green photoluminescence emission at 2.22 eV and an EPR g value of 1.953, both of which are suppressed greatly after annealing in an oxygen atmosphere. A strong red emission observed during exposure to X-rays reveals the presence of F+ centres as a consequence of the V+O. Mn/ZnO displayed enhanced H2 generation with visible light exposure, when compared to pure ZnO and annealed Mn/ZnO in the visible region, which directly correlated with the oxygen vacancy concentration. There is an interesting correlation between the intensities of the EPR lines at the g-value of 1.953 due to the oxygen vacancies, the intensity of light emitted from the exposure to X-rays, the intensity of the photoluminescence due to oxygen vacancies and the quantity of H2 produced by the photocatalytic effect when comparing the three different nanomaterials, viz. pure ZnO, Mn/ZnO before and after annealing, all having been made exactly by the same methodologies. © The Royal Society of Chemistry 2015.