The growth mechanism of layered double hydroxide (LDH) films grown in situ on steel via hydrothermal treatment is still unclear. In this study, the mechanism of Co-Al-CO3-LDH film grown in situ on a steel substrate was investigated in detail. During the hydrothermal reaction, the in situ growth process of Co-Al LDH on steel involved three steps: (1) hydrolysis of Al3+ and etching of the steel surface, (2) hydrolysis of urea and promotion of LDH nuclei, and (3) crystallization of LDH. More importantly, the generation of Al(OH)3 determined the integrity of the LDH film grown on the steel surface, and a suitable heating rate was also the key factor that affected the growth of the ordered and regular LDH nanoflakes. Therefore, this work provides a comprehensive understanding of the in situ LDH growth mechanism on steel and may facilitate optimal LDH film preparation.