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In this paper, the use of magnesium oxide (MgO) indiffusion in combination with Ti:LiNbO3 through appropriate control of pre- and post-diffusion parameters is investigated as a way of controlling optical mode size. The co-diffusion of pre-patterned Ti with various patterned MgO films on LiNbO3 has been compared experimentally. This method has been applied to study straight waveguides and couplers. The waveguides were optically characterized by near-field mode size and loss measurements methods at a wavelength of 1.55 μm. Reduction of inter-mode coupling between adjacent waveguides with the introduction of MgO has been observed.