Intermittent shear flow including start-up flow and small oscillatory amplitude time sweep or stress relaxation after cessation of shear flow was used to study the rheological behavior and internal structure of thermotropic liquid crystalline polymer (TLCP). There are two kinds of intermittent shear flow: all start-up flows are in the same direction (intermittent flow forward: IFF) and start-up flows change their directions alternately (intermittent flow reversal: IFR). The results show that the stress of start-up flow of IFF and IFR in the test process is not superposed, indicating different changes of internal structure of thermotropic LCP (TLCP). Two main factors affect structure changes in the experimental time scale. One relates to long-term texture relaxation process, the other is an interchain reaction that becomes important after 30 min. The two factors raise the stress of IFF, but express complex effects for the stress of IFR. The latter factor becomes very important at long time annealing process. The relaxation behavior was also studied by the application of wide range relaxation spectrum calculated from the combined dynamic modulus, which gave three characteristic relaxation times (0.3, 10 and 600 s) ascribable to the relaxations of less-phase orientation, domain orientation, and domain deformation, respectively. The result also shows that the domain coalescence (texture relaxation), a long relaxation time, is a much slow process and lasts beyond 2400 s of the test time.