Periodically poled crystalline materials are extremely attractive for processes such as second harmonic generation and optical parametric generation due to their very high conversion efficiency. For optimal performance, fabrication of poled regions with sub-micron tolerance is required. In this paper we introduce multi-photon laser scanning luminescence microscopy as a powerful minimally-invasive measurement technique which provides information about internal device structure with high spatial resolution that cannot be easily obtained with existing methods. A comparative study of confocal and multi-photon imaging of periodically poled crystalline materials is also performed.