An optical technique is proposed for the accurate calibration of pulsed high magnetic fields utilizing the magnetic field dependent photoluminescence (PL) properties in an Er(3+):YVO(4) single crystal at 80 K. Bright green PL emissions are excited by a 487.5 nm laser line and can be enhanced greatly by a magnetic field at certain field values (B(c)). Since the B(c)'s under 10 T are extremely stable for a given sample at a certain temperature, and the FWHM of the enhancement peaks are less than 0.9 T, an Er(3+):YVO(4) single crystal is proven to be a good candidate for pulsed high magnetic field calibration. The detailed processes and numerous advantages of the technique are presented in this work.