The isothermal and non-isothermal crystallization behavior of blast furnace (BF) slag with varying CaO/SiO2 ratios was in-situ observed through a confocal scanning laser microscopy (CLSM). The crystallization kinetics was analyzed and precipitation of crystalline phases was discussed by theoretical analysis from FactSage 8.0 and X-ray Diffraction (XRD). The results showed that, with the increasing CaO/SiO2 ratio from 1.0 to 1.3, the crystals morphology changed first from rectangles and squares to small-size and irregular, and further to long strip shape at the cooling rate of 100 degrees C/min. The onset crystallization temperature in CTT diagram was higher at a larger CaO/SiO2 ratio due to the decrease of polymerization degree of the slag. For the isothermal crystallization process at 1250 degrees C, the crystals morphology changed gradually from lamellar to long-trip or columnar, and the incubation period in TTT diagram became shorter with the increase of CaO/SiO2 ratio. Avrami index n decreased from appropriately 2.3 to 1.5, and the growth mode of crystals converted from two-dimensional to one-dimensional. XRD analysis showed that only merwinite existed in four slags at 1380 degrees C. Akermanite and gehlenite were generated at 1350 degrees C, and their amount first increased greatly and then decreased slightly with a continuous increase of CaO/SiO2 ratio. At the low temperature, the number of akermanite and gehlenite reduced, while that of merwinite increased obviously in the slags when CaO/SiO2 ratio was 1.2 and 1.3, indicating that increasing CaO/SiO2 ratio promoted the generation of merwinite.