Most near-β titanium alloy structural components should be plastically deformed at high temperatures. Inappropriate high-temperature deformed processes can lead to macro-defects and abnormally coarse grains. Ti-3Al-6Cr-5V-5Mo alloy is a near-β titanium alloy with the potential application. The available information on the high-temperature deformation behavior of the alloy is limited. To provide guidance for the actual hot working of the alloy, the flow stress behavior and processing map at α + β phase field and β phase field were studied, respectively. Based on the experimental data obtained from hot compressing simulations at the range of temperature from 700 °C to 820 °C and at the range of strain rate from 0.001 s−1 to 10 s−1, the constitutive models, as well as the processing map, were obtained. For the constitutive models at the α + β phase field and β phase field, the correlated coefficients between actual stress and predicted stress are 0.986 and 0.983, and the predictive mean relative errors are 2.7% and 4.1%. The verification of constitutive models demonstrates that constitutive equations can predict flow stress well. An instability region in the range of temperature from 700 °C to 780 °C and the range of strain rates from 0.08 s−1 to 10 s−1, as well as a suitable region for thermomechanical processing in the range of temperature from 790 °C to 800 °C and the range of strain rates from 0.001 s−1 to 0.007 s−1, was predicted by the processing map and confirmed by the hot-deformed microstructural verification. After the deformation at 790 °C/0.001s−1, the maximum number of dynamic recrystallization grains and the minimum average grain size of 17 μm were obtained, which is consistent with the high power-dissipation coefficient region predicted by the processing map.