We experimentally study the effects of UV exposure on a single-mode fiber (SMF) with a fiber multimode interferometer (MMI) based on the singlemode-multimode-singlemode-multimode-singlemode (SMSMS) fiber structure. We observe a wavelength shift of over 33 nm when irradiating the central SMF in the SMSMS fiber structure with a 3-mm-width UV beam (the UV laser has a wavelength of 193 nm and pulse energy of 3 mJ). According to our numerical simulation, the SMSMS fiber structure can achieve a very high refractive-index (RI) sensitivity of 67670 nm/RIU with a very good linearity of R2≈0.9999. The structure can find potential application for high-sensitivity RI sensing by replacing the central SMF with a hollow-core optical fiber filled with the sample under test. The UV exposure technique can be used for tuning the characteristics of fiber MMI devices.