Biofunctionalized nanocolloids offer a promising platform for creation of novel materials using addressable interactions. Crystalline phases are of especial interest for the development of novel plasmonic, magnetic, and catalytic metamaterials. When flexible single-stranded linker DNAs are added to the mixture of two types of dispersed, ssDNAs capped gold nanocolloids which are noncomplementary to each other but complementary to the respective ends of the linker DNA, a crystalline phase of body-centered cubic unit cell is formed at the premelting temperature of the system. An evolution of the structure, crystal formation, and thermodynamic path toward equilibrium state have been studied in details using in-situ small-angle X-ray scattering for different DNA linker designs.