The atomic layer deposition (ALD) technology is introduced to enhance the sensitivity of optical fiber cladding mode to surrounding refractive index (SRI) variation. The highly uniform Al2O nanofilm was deposited around the double cladding fiber (DCF) which presents cladding mode resonant feature. With the high refractive index coating, the cladding mode resonant spectrum was tuned. And the sensitivity enhancement for SRI sensor was demonstrated. Through adjusting the deposition cycles, a maximum sensitivity of 723 nm/RIU was demonstrated in the DCF with 2500 deposition cycles at the SRI of 1.34. Based on the analysis of cladding modes reorganization, the cladding modes transition of the coated DCF was investigated theoretically. With the high performance nanofilm coating, the proposed SRI sensor is expected to have wide applications in chemical sensors and biosensors.