A photonic crystal fiber (PCF) with high relative sensitivity was designed and investigated for the detection of chemical analytes in the terahertz (THz) regime. To ease the complexity, an extremely simple cladding employing four struts is adopted, which forms a rectangular shaped core area for filling with analytes. Results of enormous simulations indicate that a minimum 87.8% relative chemical sensitivity with low confinement and effective material absorption losses can be obtained for any kind of analyte, e.g., HCN (1.26), water (1.33), ethanol (1.35), KCN (1.41), or cocaine (1.50), whose refractive index falls in the range of 1.2 to 1.5. Besides, the PCF can also achieve high birefringence (∼0.01), low and flat dispersion, a large effective modal area, and a large numerical aperture within the investigated frequency range from 0.5 to 1.5 THz. We believe that the proposed PCF can be applied to chemical sensing of liquid and THz systems requiring wide-band polarization-maintaining transmission and low attenuation.