The modification of dielectric surface with a self-assembled monolayer (SAM) such as octadecyltrichlorosilane (OTS) is a widely used method to tune the electrical property of diverse electronic devices based on organic semiconductors, graphene, transition metal dichalcogenides (TMDs), and so forth. The surface roughness of self-assembled OTS monolayer is a key factor in determining its effect on device performance, but the preparation of an ultrasmooth OTS monolayer is a technologically challenging task. In this work, an ultrasmooth OTS monolayer is prepared via a facile peeling method, which may serve as a postremedy strategy to remove the protuberant aggregates. Such a method has not been reported before. With organic semiconductors as a testing model, ultrasmooth OTS may significantly improve the charge mobility of organic field-effect transistors (OFETs). P-type dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) OFET with an ultrasmooth OTS monolayer yields good reproducibility and unprecendented maximum mobility of 8.16 cm(2) V(-1) s(-1), which is remarkably superior to that of the OFET with a pristine OTS monolayer. This work develops a simple method to resolve the common and significant problem of the quality of OTS modification, which would be highly promising for electronic applications as well as other fields such as surface and interface engineering.