In recent years, solid organic materials such as silicone rubber and epoxy resin have been widely used in electrical equipment due to their excellent insulation properties. However, as a result of manufacturing and design flaws as well as aging issues during operation, the insulating materials in the linked state no longer fit tightly and tiny structural defects (defect size less than 10 mm) develop, such as debonding at the composite interface, pores or cracks within the insulating material, etc. Tiny defects are prone to partial discharges and breakdowns, compromising the safety of high-voltage power equipment, particularly when subjected to strong electric fields. Therefore, it is necessary to carry out non-destructive testing (NDT) for such tiny defects. Such defects are small in size, easily buried in the material, and even some are wrapped in metal, which in turn requires very high detection accuracy, but traditional methods are difficult to achieve, so NDT technologies for tiny defects within insulating materials have become a research hotspot in the field of electric power in recent years. This paper firstly introduces the sources of tiny defects in solid organic insulating materials for electrical equipment. Secondly, the harm caused by structural defects is elaborated. Finally, emerging NDT methods and their advantages and limitations in defect detection are described in detail. The review aims to provide the reader with a comprehensive overview of most of the NDT techniques used in the detection of tiny defects within solid organic insulating materials for electrical equipment and their most salient features.