It is well known that structural relaxation in a bulk metallic glass affects some properties such as viscosity, electrical conductivity, and ductility. The free volume in glassy alloy, which is open volume retained by rapidly solidification from liquid state, has a significant roll for those properties. In order to discuss the nature of free volume in a Zr 50Cu40Al10 bulk metallic glass, positron lifetime measurements have been performed for this metallic glass before and after annealing, and all positron lifetime spectra have been decomposed into multi components as a size distribution function by use of CONTIN-PALS II program. The positron lifetime distribution for this metallic glass has a broad spectrum comparing to crystal metal including a single vacancy, and its average lifetime corresponds to the free volume size. This width of positron lifetime (free volume size) distribution decreases by the annealing at 673 K. This change of the positron lifetime distribution can be attributed to a free volume relaxation.