The transition process from circular Couette flow to Taylor vortex flow regime was experimentally investigated by measuring the instantaneous velocity vector fields at the annular gap flow region between two concentric cylinders. The proper orthogonal decomposition method, vorticity calculation, and frequency analysis were applied in order to analyze the instantaneous velocity fields to identify the flow characteristics during the transition process. From the results, the kinetic energy and corresponding reconstructed velocity fields were able to detect the onset of the transition process and the alternation of the flow structure. The intermittency and oscillation of the vortex flows during the transition process were also revealed from the analysis of the instantaneous velocity fields. The results can be a measure of identifying the critical Reynolds number of the Taylor-Couette flow from a velocity measurement method.