In transition metal oxides, the potential of competing energetics of interacting fundamental entities is best displayed in perovskite manganites via the formation of a variety of exotic phases; however, there are limitations of extreme sensitivity to extrinsic and intrinsic defects and the slightest of structural modulations. Here, we report the effect of oxygen annealing and epitaxial strain on the ultrafast carrier excitation and relaxation mechanism in charge-ordered (CO) manganite Pr0.5Ca0.5MnO3 (PCMO) thin films of 60 and 150 nm thicknesses, both as-grown and oxygen annealed, as investigated by optical pump–terahertz (THz) probe measurements. Transient THz transmittance is negative for both films. Bi-exponential relaxation behavior accompanied with acoustic modulations was observed that varies along with strain and oxygen content of the films. As fitted by the sum of exponentials, the fast relaxation time constant is found to be fluence independent, while the slow relaxation time constant decreases with pump fluence for both films and is less for the annealed film suggesting that the relaxation in PCMO strongly depends on strain and oxygen content. This study on non-equilibrium carrier dynamics depicting the sensitivity of defects and subtle structural modifications is unprecedented in demonstrating the ultrafast control of CO manganites.