We report on a new non-destructive electrical fault isolation (EFI) technique to localize interconnection failures in through-silicon via (TSV) structures for three-dimensional (3-D) integration. The scanning optical microscopy (SOM) technique is based on light-induced capacitance alteration (LICA) and uses localized photon probing of TSV interconnect capacitance to localize interruptions of electrical connectivity. The technique is applicable to passivated devices and allows rapid, efficient, and non-destructive fault isolation at wafer level. We describe the physics behind signal generation of the technique and demonstrate the TSV photocapacitance effect. We further demonstrate the LICA technique on open failed TSV daisy chain structures and confirm our results with microprobing and voltage contrast measurements in a scanning electron microscope (SEM).