A core-removed D-shaped structure with different residual thickness (RT) was manufactured on a single mode silica fiber (SMF) to enhance the sensitivity by using of ultra-precise polishing technology. With six different RTs ranging from ∼55 µm to ∼28 µm, the RT enhancement effect in a D-shaped SMF was researched in detail. The influence of the RT on its transmission spectra was investigated both theoretically and experimentally. Considering a compromise between the multimode interference efficiency and optical power loss, an optimum RT value of 34.09 µm was achieved. The obtained refractive index (RI) sensitivity was 10243 nm/RIU in the RI range of 1.430-1.444, corresponding to a RI resolution of 1.9×10-6 RIU. A high-performance all-fiber sensor was developed to monitor the evaporation process volatile organic compounds (VOCs) based on the RT-enhanced D-shaped SMF. As proof of concept, a 2-hour continuous monitoring was carried to monitor the chloroform and alcohol mixture. As a result, the evaporation of alcohol and chloroform were clearly identified and monitored. The developed RT-enhanced D-shaped fiber sensor provides an alternative way for chemical process monitoring and industrial applications.