This paper describes progress in characterizing the distribution and localization of the second-order nonlinearity induced in thermally poled silicate glasses and optical waveguides, in particular, optical fibers. It starts by describing the basics of the poling technique, especially the most commonly used “thermal poling” technique. Then results of systematic investigation of the distribution of the second-order nonlinearity in poled glass and special fibers using second-harmonic microscopy are presented. Interesting issues such as the effectiveness of the poling technique for waveguides formed by ultrafast laser pulses are also discussed.