Currently, the fish-scaling resistance of most hot-rolled enamel steels is improved by adding Ti to form fine TiC carbides as hydrogen traps. Given that the hydrogen capture capacity of NbC is higher than that of TiC, the manufacture of hot-rolled enamel steels via Ti-Nb microalloying has a promising future. In the present study, a Ti-Nb microalloyed hot-rolled enamel steel was developed, and its microstructure, mechanical properties, and fish-scaling resistance were studied by optical microscopy, transmission electron microscopy, tensile test, and hydrogen permeation test. The results show that the microstructure of hot-rolled experimental steel is composed of ferrite and fine carbides, with a large number of fine precipitates uniformly distributed in the ferrite grains. After the first and second enamel firings, the average sizes of ferrite grain and precipitates gradually increase, the yield strength decreases from 711 ± 9 MPa to 471 ± 17 MPa and 409 ± 8 MPa, the tensile strength decreases from 761 ± 7 MPa to 524 ± 15 MPa and 490 ± 12 MPa, and the elongation increases from 21.0 ± 2.8% to 27.8 ± 1.8% and 33.9 ± 1.1%. The hydrogen permeation value (TH value) decreases from 35.9 min/mm2 to 6.8 min/mm2 and 3.9 min/mm2 after the first and second enamel firings. That is, the fish-scaling resistance of hot-rolled experimental steel is significantly reduced after enamel firing, which is caused by the coarsening of precipitates, resulting in a significant reduction in the density of irreversible hydrogen traps (from 1.21 × 1025 cm−3 to 6.50 × 1023 cm−3 and 4.27 × 1023 cm−3). A large amount of semi-coherent precipitates is the key to obtaining the good fish-scaling resistance of hot-rolled enamel steel.