The non-catalytic preparation of high-quality vertical graphene nanowalls (VGN) and graphene-based high output power hydrovoltaic effect power generation devices has always been difficult to achieve. In this work, we successfully prepared VGN with defect density, few layers and submicron domain size on a variety of substrates without catalysts through reasonable adjustment of growth conditions by the hot-wire chemical vapor deposition (HWCVD) method. The Raman test of the VGN prepared under optimal conditions showed that its ID/IG value was less than 1, and I2D/IG was more than 2.8. The deposition pressure was a key factor affecting the crystallization quality of the VGN. A suitable deposition pressure of 500 Pa could screen the active carbon clusters involved in the growth of nanowalls. The VGN prepared had excellent electrical properties and output of dropping-ion-droplet nano-power generation devices. Because of the larger crystal domain area and smaller contact angle of the VGN, the maximum output power exhibited at 100 Pa was 15.7 μW, which exceeded the value produced by other reported hydrovoltaic energy harvesting devices. All of them confirmed that VGN with improved quality had high application prospects in nano-energy devices.