Optical fiber sensors are of great interest due to their intrinsic advantages over electronic sensors. In this work, the sensing characteristics of two different and novel optical fiber devices are compared, after simultaneously depositing a thin-film using the layer-by-layer assembly deposition process. The first one is an SMS structure, formed by splicing two single-mode fiber pigtails on both sides of a coreless multimode fiber segment. This structure induces an interferometric phenomenon that generates several attenuation and transmission bands along the spectrum. These bands are sensitive to variations in the surrounding refractive index, although this sensitivity has been enhanced by a TiO2/PSS thin-film. The other device is a 40 mm uncladded segment of a 200 μm-core multimode optical fiber. When coated by a TiO2/PSS thinfilm, part of the light transmitted into the uncladded core is coupled into the thin-film, generating a lossy mode resonance (LMR). The absorption peaks due to these phenomena red-shift as long as the thin-film thickness increases or the external RI becomes higher. The performance of these devices as refractometers and relative humidity sensors are tested. Results show that the LMR-based sensor is more sensitive in both situations, in spite of its lower sensitivity. Particularly, it presents a 7-fold sensitivity enhancement when measuring surrounding medium refractive index changes and a 10-fold sensitivity enhancement when measuring environmental relative humidity. To our knowledge, this is the first time that a comparative study between SMS and LMR sensors is performed.