Titanium alloy is widely used for manufacturing structural parts of high-end equipment due to its excellent mechanical properties, despite difficulty in being machined. Nowadays, titanium alloy parts are mostly machined by ball-end milling cutters (BEMC), but the cutting edge structure of the BEMC limits the improvement in machining efficiency and surface quality of the parts. In this paper, a circular-arc milling cutter (CAMC) with large-curvature cutting edge was proposed; the differential geometry method was used for establishing the geometric model for the contour surface of the CAMC and the mathematical model for the spiral cutting edge line; the conversion matrix between grinding wheel and workpiece coordinates was introduced to derive the equation of grinding wheel trajectory when the rake face of the CAMC was ground; the self-designed CAMC was ground and tested in accuracy. The comparative research was conducted experimentally on the side milling of titanium alloy TC4 with the CAMC and BEMC, and consequently the variation laws of milling forces, wear morphology and machined surface quality were obtained about the two types of milling cutters. The results indicated that the CAMC can effectively reduce the main milling force and keep the milling process stable. Moreover, the CAMC was worn slower and produced better surface quality than the BEMC.