The authors present a detailed theoretical analysis of two-photon resonant third- and fifth-harmonic generation in metal vapors with picosecond laser pulses. These processes are described by self-consistent Maxwell-Bloch equations which take into account the effects of optical Stark shifts, multiphoton ionization, Doppler broadening, two-photon absorption, the reaction of the third-harmonic field on the fundamental, and a nonlinear index of refraction. As an example, a quantitative analysis of third- and fifth-harmonic generation in lithium vapor (2s-4s transition) is presented. The limitations on energy conversion efficiency and the temporal as well as spectral characteristics of the harmonic pulses are investigated for two kinds of low-loss propagation fundamental pulses. It is shown that 90° phase-shifted fundamental pulses (zero area) are more efficient than 2m pulses. Energy conversion efficiencies of 6.5% for third-harmonic (190 nm) and 0.07% for cascade fifth-harmonic (114 nm) pulses are predicted. © 1979 The American Physical Society.