A new technique, direct photodegradation of self-assembled monolayers (SAM), to obtain surface energy gradients on Si substrates was demonstrated. The gradient surface, with hydrophobic to hydrophilic gradients, was prepared by two steps: Firstly, a homogeneous fluoroalkylsilane SAM film was deposited by a chemical vapor deposition on a Si substrate. Secondly, a controlled photodegradation technique was directly applied to the homogeneous FAS-SAM surface. The surface energy gradient was then obtained due to the different intensity of photoirradiation in the different positions along the photodegraded path on the SAM surfaces. The resulting surface displayed a gradient of wettability (with the contact angle of water changing from 55° to 18°) over a distance of 4.2 mm. The water droplet was driven by surface energy gradient and spontaneously moved from the hydrophobic to hydrophilic surface. During the moving process, the water droplet accelerated firstly and then decelerated. The peak velocity was about 23.3 mm/s. The velocity is dependent on the gradient of the surface energy.