This paper experimentally studies the effect of transonic flow on local heat transfer coefficients and film cooling effectiveness distributions of a turbine vane’s suction surface with compound-angle shaped-hole configuration. A Temperature Sensitive Paint (TSP) method is used to determine the local heat transfer coefficients and film cooling effectiveness simultaneously. Tests were performed in a five-vane annular-sector cascade blow-down facility. The exit Mach numbers are controlled to be 0.7 and 0.9, from subsonic to transonic conditions. Compressed air is used as coolant with a coolant-to-mainstream density ratio 0.91 on film cooling and heat transfer study. Three averaged coolant-to-mainstream blowing ratios in the range, 0.7, 1.0, and 1.6 are investigated. The test vane features three rows of radial-angle cylindrical holes around the leading edge, and two rows of compound-angle shaped holes on the suction side. Effects of blowing ratio and exit Mach number on the vane suction surface heat transfer and film cooling effectiveness distributions are obtained, and the results are presented and explained in this investigation.