Reaction pathways in the synthesis of three photorefractive silicates—γ‐Bi12 SiO20 (BSO), γ‐Bi12 GeO20 (BGO), and gamma‐Bi12 TiO20 (BTO)—were systematically investigated. The main results were as follows: (i) all the reactions of the form 6Bi2O3+ MO2→> γ‐Bi12 MO20 (SR1 for M = Si, SR2 for M = Ge, SR3 for M = Ti) in the solid state seemed to be diffusion‐controlled processes and were affected by both temperature and time, where the reaction temperature increases in the order SR1 < SR2 < SR3; (ii) the metastable phases Bi2 SiO5 (tetragonal) in reaction SR1, Bi2 GeO5 (orthorhombic) in reaction SR2, Bi4 Ti3 O12 (orthorhombic) in reaction SR3 may be formed and seemed to greatly accelerate the above‐mentioned solid‐state reaction processes; and (iii) for a continuous heating process, pure γ‐Bi12 SiO20 and γ‐Bi12 GeO20 could be produced before melting, whereas pure γ‐Bi12 TiO20 could not be produced, even if all the mixed phases had melted.