Although one of the simplest methods, various must be resolved before industrializing material jetting technology to fabricate low-temperature co-fired ceramics (LTCC). This research examines related glass-ceramic ink configurations and multi-material jet-sintering. Firstly, we present a method for obtaining a nanoscale borosilicate glass powder via radio frequency plasma spheronization, and its surface is grafted with acrylate molecules to create a jettable nanosol. By fusing this configured glass nanosol with silica nanosol in the typical glass-ceramic LTCC combination (4:6) and adding suitable photosensitizing elements, it can be configured into light-curable LTCC inks. 3D printing of multilayer structures using a multi-material jetting device provides a three-layer structure of ceramic layer - conductive layer - ceramic layer, with the ceramic layer cured by ultraviolet light and the conductor pattern scanned and surface-dried by a laser to obtain high-precision delivery of the green part. The sintering effect between different materials is intact and synchronized shrinkage is achieved. Conductivity tests during the sintering stage yielded high conductivity values up to 1.43 × 107 S/m, which further provides the microscopic morphology of the two embedded wires, and the complete and continuous results demonstrate the effectiveness of multilayer wire fabrication. The nanopowder, sol-gel configuration and material jetting under multiple energy loading proposed in this paper significantly support the LTCC additive manufacturing route.