In the envelope-function approximation, interband transitions produced by electric fields are neglected. However, electric fields may lead to a spatially local (k-independent) coupling of band (internal, pseudospin) degrees of freedom. Such a coupling exists between heavy-hole and light-hole (pseudo-)spin states for holes in III-V semiconductors, such as GaAs, or in group IV semiconductors (germanium, silicon, ...) with broken inversion symmetry. Here, we calculate the electric-dipole (pseudospin-electric) coupling for holes in GaAs from first principles. We find a transition dipole of 0.5 debye, a significant fraction of that for the hydrogen-atom 1s → 2p transition. In addition, we derive the Dresselhaus spin-orbit coupling that is generated by this transition dipole for heavy holes in a triangular quantum well. A quantitative microscopic description of this pseudospinelectric coupling may be important for understanding the origin of spin splitting in quantum wells, spin coherence/relaxation (T * 2 /T1) times, spin-electric coupling for cavity-QED, electric-dipole spin resonance, and spin non-conserving tunneling in double quantum dot systems.