The penetration diffusion of ultrafine Portland cement (UPC) slurry is closely related to its rheological behaviour and micro-flocculation structure. To date, there has been a need for more research investigating the impact of mixing parameters on the macro-micro hydrodynamic behaviour of UPC slurries. In this study, a series of macroscopic rheomechanical characterisation tests and microscopic in-situ tests of the flocculation structure of UPC slurries under various mixing parameters were conducted systematically by using a rotational rheometer and a focused beam reflectance measurement (FBRM) system. The effects of mixing speeds and times on the macroscopic shear stress-shear rate curves, rheological patterns, rheomechanical parameters, and the distribution of micro-flocculated particles of UPC slurries were investigated. The results indicate that the macroscopic rheomechanical parameters and microscopic flocculation coefficient of UPC slurry exhibit a decrease with increased slurry mixing speed. However, a “decrease and then increase” trend is observed with increased slurry mixing time. The smaller the powder size of cement and the lower the water-cement ratio of the slurry, the more sensitive the rheomechanical properties of the slurry are to the influence of the mixing parameters. A positive correlation exists between the macroscopic rheomechanical properties of UPC slurry and its microscopic flocculation coefficient. Increasing the slurry mixing speed or prolonging the early mixing time can destroy the microscopic flocculation particles of UPC slurry, a reduction in the flocculation coefficient of the slurry, and an improvement in the macroscopic fluidity properties. The research findings provide a foundation for improving the effectiveness of UPC grouting in the engineering field.