We report measurements and the results of calculations demonstrating that the annihilation dynamics of positronium (Ps) atoms can be controlled by Stark and Zeeman mixing of optically excited states. In the experiments a trap-based pulsed positron beam was employed to generate a dilute Ps gas with a density of ∼10 7 cm −3 using a porous silica target. These atoms were excited via 1 3 S 1 → 2 3 P J transitions in parallel electric and magnetic fields using a nanosecond pulsed dye laser, and Ps annihilation was measured using single-shot lifetime spectroscopy. The composition of the excited n = 2 sublevels was controlled by varying the polarization of the excitation laser radiation and the strength of the electric and magnetic fields in the excitation region. The overall decay rates of the excited states can vary by a large amount, owing to the enormous differences between the annihilation and florescence lifetimes of the accessible field-free states. The energy-level structure, spectral intensities, and florescence and annihilation lifetimes in the presence of the fields were determined from the eigenvalues and eigenvectors of the complete n = 2 Hamiltonian matrix in an |nS J M J basis. Using these data as the input to a Monte Carlo model yielded calculated values which could be compared with experimentally measured quantities; qualitative agreement with the measurements was found. Varying the electric field in the presence of a weak parallel magnetic field provides control over the amount of level mixing that occurs, making it possible to increase or decrease the Ps lifetime. Field-controlled Ps decay can be used as an ionization-free detection method. Conversely, increasing the excited-state lifetime can potentially be exploited to optimize multistep excitation processes using mixed intermediate states. This will be useful either in minimizing losses through intermediate-state decay during excitation or by making it possible to separate excitation laser pulses in time. In addition, the adiabatic extraction of appropriate eigenstates from the electric field in which they are excited can, in principle, be used to prepare pure 2 3 S 1 atoms. The availability of atoms in these states produced via single-photon excitation will facilitate high-resolution microwave spectroscopy of the Ps n = 2 fine structure.