The non-minimal coupling of a scalar field is considered in the framework of Ashtekar's new variables formulation of gravity. A first order action functional for this system is derived in which the field variables are a tetrad field, and an SL(2,C) connection, together with the scalar field. The tetrad field and the SL(2,C) connection are related to the Ashtekar variables for the vacuum case by a conformal transformation. A canonical analysis shows that for this coupling the equations of Ashtekar's formulation of canonical gravity are non-polynomial in the scalar field. (to be published in Phys. Rev. D)