5-Hydroxymethylfurfural (HMF) is a promising platform chemical for production of value-added chemicals and fuels. Conversion of abundantly available and cheap sucrose for HMF synthesis was systematically investigated in the present study. Results showed that Lewis acid AlCl3 is effective in catalytic transformation of sucrose. Combining AlCl3 with different Bronsted acids, no matter whether they were inorganic acids (HCl, H2SO4, and H3PO4) or organic acids (malic acid, succinic acid, and oxalic acid), or variation of ratio of Lewis acid/Bronsted acid represented by AlCl3/HCl, did not change the obtained maximum HMF yields compared with AlCl3 alone, but shortened the time required to reach the maximum HMF yield. Sucrose conversion in a green reaction media of aqueous γ-valerolactone (GVL) solvent resulted into comparable HMF yields with dimethyl sulfoxide (DSMO)-water system. Addition of monovalent salt NaCl and divalent salt Na2SO4 produced opposite effect with Cl− promoting while SO42− inhibiting HMF production. Furthermore, HMF synthesis from constituent monosaccharides of sucrose and molasses, a by-product from sugar manufacturing process, was also carried out and it was found that an equivmole mixture of glucose and fructose gave rise to almost identical HMF yield to the same mole of sucrose. Molasses, even after chemical pretreatment for removal of certain amount of inorganic salts and color substances, was significantly inferior to synthetic molasses in terms of HMF formation, indicating the complexity and difficulty in chemical valorization of molasses for production of platform molecules.