We study both the classical and quantum rotational dynamics of an asymmetric top molecule, controlled through three orthogonal electric fields that interact with its dipole moment. The main difficulties in studying the controllability of these infinite-dimensional quantum systems are the presence of severe spectral degeneracies in the drift Hamiltonian and the nonsolvability of the stationary free Schrodinger equation, which lead us to apply a perturbative Lie algebraic approach. In this paper we show that, while the classical equations given by the Hamiltonian system on SO(3) x R-3 are controllable for all values of the rotational constants and all dipole configurations, the Schodinger equation for the quantum evolution on L-2 (SO(3), C) is approximately controllable for almost all values of the rotational constants if and only if the dipole is not parallel to any of the principal axes of inertia of the asymmetric rigid body.