The confined phase behaviors of microencapsulated normal hexadecane/octadecane mixtures (abbreviated as m-C-16/C-18) have been investigated by combination of differential scanning calorimetry and in situ wide-angle X-ray scattering. The binary alkane mixtures confined in three-dimensional geometrical space demonstrate two novel crystallization features. The surface freezing is significantly enhanced after C-16/C-18 mixtures being encapsulated, and the surface monolayer formed is proved to be an ideal solid solution composed by C-16 and C-18. Furthermore, m-C-16/C-18 mixtures are trapped into a stabilized rotator phase below the crystallization temperatures, whereas C-16/C-18 mixtures with certain compositions form the low-temperature crystalline structure directly. These confined crystallization features originate from the jointed effects of spatial confinement and chain mixing of the components. Moreover, the phase diagram of the confined binary alkane mixtures (m-C-16/C-18) is successfully established for the first time, which enlightens the crystallization features of other spatially confined soft-matter binary systems.