The excitation of metastable hydrogen towards the n = 4 Stark manifold is investigated both theoretically and experimentally. The Stark Hamiltonian is diagonalized to obtain the energy levels, oscillator strengths and relaxation rates of the n = 2 and n = 4 Stark states. In a fast beam experiment, the transitions are excited by the blue line of a CW argon ion laser with appropriate Doppler detuning, and the measured transition frequencies agree well with the calculated values. The population of the 4s state, as measured by its fluorescence, is maximum for an electric field strength between 50 and 100 V cm⁻¹, and a laser polarization perpendicular to the static field.