We present photoexcitation experiments indicating that efficient CH(A) emission from irradiated ground state methylene can be observed only if energies of more than 9.5 eV have been deposited in the CH2(1 B-3(1)) radical although according to energy considerations and adiabatic potentials 7.3 eV should be sufficient to generate CH(A). Theoretical studies on the photodissociation process using potential energy surfaces obtained with highly correlated quantum chemical methods and surface hopping techniques have been applied to understand the experimental observations.