We have used combinations of light, heat, and electrostatic fields to investigate the orientation of nonlinear azo-chromophores chemically incorporated into high glass transition temperature (T-g) polyimides. A number of nonlinear optical polyimides have been synthesized in which the interaction between the nonlinear optical chromophore and the polymer main chain was systematically altered to determine to what extent this steric interaction influences the orientation of the nonlinear chromophore. Chromophores in polymers may be oriented by a number of methods : (a) polarized light at room temperature (i.e., photo-induced orientation or PIG), (b) polarized light and electric fields (i.e., photo-assisted poling or PAP) at temperatures ranging from room temperature to the polymer T-g, and (c) electric fields at T-g (thermal poling). While thermal poling and PIO are usually possible, PAP depends strongly on the molecular structure of the polymer. Previously we have shown that PIO can be accomplished at room temperature in a system where the nonlinear chromophore is embedded into the polyimide main chain via the donor substituent, and this orientation can only be thermally erased at temperatures approaching T-g. In this article we show that, whereas photoisomerization can efficiently depole donor-embedded polyimides in a matter of few minutes at room temperature, PAP does not induce any polar order. This behavior is in marked contrast to a structurally related, side-chain, nonlinear polyimide, in which the azo chromophore is tethered via a flexible linkage to the polymer backbone. In this case some PAP occurs even at room temperature, while no PAP is observed for a donor-embedded system with a similar T-g. We suggest that the orientation during PAP below T-g in the side-chain polyimide is primarily due to the movement of the azo side chains, and there is a very little coupling of this motion to the main chain.