In this work, a high-sensitivity distributed lateral pressure sensor based on Brillouin Optical Time-Domain Reflectometry (BOTDR) technique is proposed to enhance the pressure sensitivity using a double-coated Single-Mode Fiber (SMF). Firstly, a pressure-induced strain model is developed to analyze the enhancement mechanism of pressure sensitivity by Brillouin Frequency Shift (BFS). With increasing of outer coating radius, or with decreasing of the Young’s modulus and Poisson’s ratio of outer coating, the lateral pressure sensitivity increases. By using a double-coated SMF whose outer coating radius is 1500 μm, a high sensitivity of -3.51 MHz/MPa in the range of 0-30 MPa is achieved, which is about five times higher than that of single-coated SMF. At a spatial resolution of 1.5 m, the maximum measurement error of the proposed pressure sensing system is less than 0.09 MPa.