The construction of multiple light guidance mechanisms in a hollow-core fiber (HCF) structure is a popular way to realize the simultaneous measurement of multiple parameters. In this work, a partial coating method to excite multiple anti-resonant light guidance mechanisms (ARLGMs) in an HCF structure for the simultaneous measurement of multiple parameters is proposed. As an example, a double ARLGM based on a partially polyimide (PI)-coated HCF structure for the simultaneous measurement of relative humidity (RH) and temperature is demonstrated theoretically and experimentally. The dip (dip II) produced by the PI-coated HCF section shifts linearly with surrounding RH changes with a sensitivity of circa 58.6 ± 0.77 pm/%RH, while the dip (dip I) produced by the bare HCF section (with an air coating layer) is insensitive to RH changes. In addition, both types of dips have linear responses to temperature variations, with similar sensitivities of ∼ 17 pm/°C. Hence, the proposed sensor structure can be used as an RH sensor that is also capable of compensating for local temperature fluctuations. More importantly, the simultaneous measurement of multiple parameters (such as biomarkers) is possible using the proposed method provided the proper sensing materials are partially coated onto the HCF surface.