Chemical sensors based on optical microresonators have been demonstrated highly sensitive by monitoring the refractive index (RI) changes in the surrounding area near the resonator surface. In an optical resonator, the Whispering Gallery Modes (WGMs) with high quality (Q) factor supported by the spherical symmetric structure interacts with the contiguous background through evanescent field. Highly sensitive detection can be realized because of the long lifetime of the photons. The computational models of solid glass microspheres and hollow glass spheres with porous wall (PW-HGM) were established. These two types of microresonators were studied through simulations. The PWHGM resonator was proved as an optimal chemical sensor and verified by experiments and compared for chemical vapor detection. The simulation and experimental results agreed well in the sensing trends for PW-HGM microresonator.