Highly active metal chlorides grafted on silicoaluminophosphate number 5, MClx/SAPO-5 (M = Cu, Co, Sn, Fe and Zn) catalysts via simple grafting of respective metal chlorides (MClx) onto SAPO-5 are reported. The study shows that thermochemical treatment after grafting is essential to ensure the formation of chemical bondings between MClx and SAPO-5. In addition, the microscopy, XRD and nitrogen adsorption analyses reveal the homogeneous distribution of MClx species on the SAPO-5 surface. Furthermore, the elemental microanalysis confirms the formation of Si−O−M covalent bonds in ZnClx/SAPO-5, SnClx/SAPO-5 and FeClx/SAPO-5 whereas only dative bondings are formed in CoClx/SAPO-5 and CuClx/SAPO-5. The acidity of MClx/SAPO-5 is also affected by the type of metal chloride grafted. Thus, their catalytic behavior is evaluated in the acid-catalyzed acylation of 2-methylfuran under novel non-microwave instant heating conditions (90−110 °C, 0−20 min). ZnClx/SAPO-5, which has the largest amount of acidity (mainly Lewis acid sites), exhibits the best catalytic performance (94.5% conversion, 100% selective to 2-acetyl-5-methylfuran) among the MClx/SAPO-5 solids. Furthermore, the MClx/SAPO-5 solids, particularly SnClx/SAPO-5, FeClx/SAPO-5 and ZnClx/SAPO-5, also show more superior catalytic performance than common homogeneous acid catalysts (H2SO4, HNO3, CH3COOH, FeCl3, ZnCl2) with higher reactant conversion and catalyst reusability, thus offering a promising alternative for the replacement of hazardous homogeneous catalysts in Friedel−Crafts reactions.