The transformation of carbides in a 1.9Cr-1.4Mo-0.3 V secondary hardening steel that was subjected to over-ageing at 600°C-700°C has been investigated. The carbides were characterized using scanning electron microscope (SEM), x-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and transmission electron microscopy (TEM) preformed on carbon replicas. The results indicate that MC, M 2 C, and M 3 C were formed during over-ageing from 600 to 700°C, whereas M 7 C 3 , and M 23 C 6 started to be formed at 650 and 700°C, respectively. In addition, the co-existence of hexagonal and orthorhombic M 7 C 3 structures in a carbide particle was firstly observed. M 3 C was transformed to other carbides, and the formation of both M 2 C and M 23 C 6 may follow the 'separate nucleation' mechanism, whereas M 7 C 3 was transformed from M 3 C via the 'in situ nucleation' mechanism. The crystallographic orientation relationships between the in situ transformed M 7 C 3 and M 3