The influences of B2O3and R2O on the structure and crystallization of CaO–Al2O3based F-free mold flux were investigated by Raman Spectroscopy and Differential Scanning Calorimetry Technique, respectively, for developing a new type of F-free mold flux. The results of structural investigations showed that B3+is mainly in the form of [BO3]. And [BO3] appears to form BIII–O–Al linkage which will produce a positive effect on forming [AlO4] network. The number of bridging oxygen and the degree of polymerization of [AlO4] network structure for CaO–Al2O3system were also increased with the increasing of B2O3. On the contrary, with the addition of R2O into CaO–Al2O3–B2O3system, the number of bridging oxygen and the degree of polymerization of [AlO4] network were decreased. DSC results showed that the crystallization process became more sluggish with the increase of B2O3, which indicated that the crystallization ability was weakened. While the quenched mold fluxes crystallized more rapidly when introducing R2O. In other word, the crystallization rates of CaO–Al2O3based slags were accelerated by the introduction of R2O. The liquidus temperature and crystallization temperature were decreased with the increasing amount of B2O3or by addition of R2O into CaO–Al2O3system. Only one kind of crystal was precipitated in 8% B2O3and %R2O-containing samples, which was CaAl2O4identified by SEM-EDS. When the content of B2O3increased from 8% to 16%, Ca3B2O6is clearly observed, demonstrating that the crystallization ability of Ca3B2O6is enhanced by the increasing concentration of B2O3in mold flux. The Ca/Al ratio of the generated calcium aluminate has been altered from 1:2 to 1:4 with the increasing of B2O3. The size of CaAl2O4crystal is gradually increased with the addition of R2O. The crystallization ability of CaAl2O4is promoted by R2O.