An efficient and safe method is proposed for the preparation of an oximesilane compound having a group of the general formula --O--N.dbd.CR.sup.2 R.sup.3, in which R.sup.2 and R.sup.3 are each a hydrogen atom or a monovalent hydrocarbon group, bonded to the silicon atom. The method consists of successive steps of which the first is for the reaction of a chlorosilane compound with ammonia and the second is for the reaction of the reaction mixture coming from the first step with an oxime compound to introduce the oxime groups as bonded to the silicon atom. Different from conventional methods in which formation of an explosive compound such as hydrochloride of an organic base or oxime compound is unavoidable, the inventive method does not involve formation of such an explosive by-product so that the desired oximesilane compound can be obtained without the danger of explosion.