In this work, we fabricated three carbon nanoplume structured samples under different temperatures using a simple hot filament physical vapor deposition (HFPVD) process, and investigated the role of surface morphology, defects, and graphitic content on relative humidity (RH) sensing performances. The Van der Drift growth model and oblique angle deposition (OAD) technique of growing a large area of uniformly aligned and inclined oblique arrays of carbon nanoplumes (CNPs) on a catalyst-free silicon substrate was demonstrated. The optimal growing temperature of 800 °C was suitable for the formation of nanoplumes with larger surface area, more defect sites, and less graphitic content, compared to the other samples that were prepared. As expected, a low detection limit, high response, capability of reversible behavior, and rapid response/recovery speed with respect to RH variation, was achieved without additional surface modification or chemical functionalization. The holes’ depletion has been described as a RH sensing mechanism that leads to the increase of the conduction of the CNPs with increasing RH levels.