They were Kareen Marie Malcolm (61) and James Lennon Malcolm (61), both of Invercargill.
Emergency services were called to the crash scene on the Riverton-Wallacetown Highway (State Highway 99), between Taramoa Rd and Price Rd, about 1.30pm.
Mr Malcolm died at the scene and Mrs Malcolm was airlifted to Dunedin Hospital but succumbed to her critical injuries.
Emergency service staff told the Otago Daily Times the crash was between a Fonterra truck and a motorcycle.
A spokeswoman for the dairy company confirmed one of the vehicles involved in the crash belonged to Fonterra.
She said the driver was not injured.
A police spokeswoman said yesterday no charges as yet had been laid and inquiries were still being conducted.