Every year, millions of people die of starvation.

Literal

Every-year millions [called-という] people [subject-が] starvation [by-で] are-dying.

何百万という ('as many as millions') uses という after a number expression to convey staggering magnitude. 飢えで marks the cause of death with で. 死んでいる with ている frames the dying as an ongoing global state of affairs.