NON-INVASIVE photoresponse (photocurrent/voltage, reflectance and transmittance) from ferroelectric thin films and memory capacitors, with its strong dependence not only on the remanent polarization, but also on the film microstructure, crystal orientation, and nature of the interfaces (state of formation/degradation, etc.) offers an excellent “tool” for probing the ferroelectric capacitors at virtually any stage of fabrication, including on-line quality control. In fact, simultaneous measurement of spectral photoresponse and spectral reflectance, as a distinctive signature of the device probed, is an ideal, high speed, non-invasive means of evaluation for such thin films at high spatial resolution (∼ 100 nm) using beam scanning. This paper discusses three aspects of such evaluation. First, the spectral transmittance of the film as a direct function of the microstructure, second, the use of band-gap illumination (365 nm) to condition a fatigued capacitor; and third, the optical E field interaction with the ferroelectric capacitor, yielding a high speed photoresponse which is related to the remanent polarization and the operational history (status of internal fields) of the ferroelectric capacitor. Combined, these different kinds of photoresponses provide a good signature of the device quality.