To realize process intensification of clean fuel production is becoming a hot topic for sustainable development. This work presents a new intensification technology of sulfuric acid alkylation of isobutane and butene using a microstructured chemical system. A microstructured chemical system has been designed and constructed. The reaction performance was determined, and the effect of acid concentration, phase ratio, reaction temperature, and ratio of isobutane to butene (I/O) were investigated carefully. The results show that the microsturctured chemical system could obviously improve the quality of alkylates with much smaller size reactor and much shorter reaction time for better transport performances. The conversion of olefin could be as high as 100% within 30 s. The selectivity of C8 was 71% with a research octane number (RON) 94.4 under the 94 wt % H2SO4. No obvious changes of H2SO4 concentration was observed after several cycles, indicating that the acid consumption could be effectively reduced in this microreaction process.