In order to solve the difficulty of precision measurement of small hole diameters with large depth-to-diameter ratios, a new measurement method based on spherical scattering electrical-field probing (SSEP) was developed. A spherical scattering electrical field with identical sensing characteristics in arbitrary spatial directions was formed to convert the micro gap between the probing-ball and the part being measured into an electrical signal. 3D non-contact probing, nanometer resolution, and approximate point probing—which are key properties for high measurement precision and large measurable depth-to-diameter ratios—were achieved. A specially designed hole diameter measuring machine (HDMM) was developed, and key techniques, including laser interferometry for macro displacement measurement of the probe, multi-degree-of-freedom adjustment of hole attitude, and measurement process planning, are described. Experiments were carried out using the HDMM and a probing sensor with a ϕ3-mm probing ball and a 150-mm-long stylus to verify the performance of the probing sensor and the measuring machine. The experimental results indicate that the resolution of the probing sensor was as small as 1 nm, and the expanded uncertainty of measurement result was 0.2 μm (k = 2) when a ϕ20-mm ring gauge standard was measured.