In this paper, composite micro-structures of Vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine) (VOPcPhO) and Poly (3-hexylthiophene-2,5-diy1) (P3HT) complex with nano-porous surface morphology have been developed by electro-spraying technique. The structural and morphological characteristics of the VOPcPhO:P3HT composite films have been studied by field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The multidimensional VOPcPhO:P3HT micro-structures formed by electro-spraying with nano-porous surface morphology are very promising for the humidity sensors due to the pore sizes in the range of micro to nano-meters scale. The performance of the VOPcPhO:P3 HT electro-sprayed sensor is superior in term of sensitivity, hysteresis and response/recovery times as compared to the spin-coated one. The electro-sprayed humidity sensor exhibits 3 times and 0.19 times lower hysteresis in capacitive and resistive mode, respectively, as compared to the spin-coated humidity sensor. (C) 2016 Elsevier B.V. All rights reserved.