A new pulsed mono-energetic slow positron beam as well as the conventional positron annihilation lifetime spectroscopy (PALS) have been applied to study the sub-surface and the bulk of epoxy polymer. Significant changes of o-Ps parameters were found at a short distance from the surface. The lifetime of o-Ps was observed to decrease with increasing the positron implantation depth, while its intensity increased. The temperature effect on o-Ps parameters at sub-surface was also investigated. The glass transition temperature for the sub-surface was lower than that for the bulk. Furthermore, the thermal expansion coefficient of the sub-surface was found smaller than that of the bulk.