External stimulation of the skin by ultraviolet B (UVB) radiation induces oxidative stress or inflammation, causing skin aging and skin cancer. Glycyrrhiza uralensis (licorice) has been used as a medicinal plant for its antioxidant, anti-inflammatory, antiviral, antimicrobial, anticarcinogenic, and hepatoprotective properties. The present study analyzed the effects of thermal processing on the bioactivities of licorice. Heat-treated licorice (HL) extracts had better antioxidant and anti-inflammatory activities than nontreated licorice (NL) extract. HL extracts also had higher total phenol contents than NL extract. In particular, contents of isoliquiritigenin, an antioxidant and anti-inflammatory substance of licorice, increased in proportion to the skin-protection effects of HL extracts. Heat treatment increased the contents of phenolic compounds such as isoliquiritigenin in licorice extract, which improved the UV photoprotective effect of licorice in human dermal fibroblasts.