In this paper, we proposed a new type high sensitive volatile organic compounds (VOCs) gas sensor array that is based on the pulse width modulation technique. Four different types of solvatochromic dyes and two different types of polymers, were used to make the five different types of sensing membranes. These were deposited on the five side-polished optical fibers by a spin coater to make the five different sensing elements of the array. In order to ascertain the effectiveness of the sensors, five VOC gases were tested. Finally, principal component analysis (PCA) has been used to discriminates different types of VOCs.