Direct white-light (CIE coordinate of x = 0.333, y = 0.335, CCT of 5455 K and CRI of 82) with a high luminous efficiency (18.4%) was achieved in the first example of Eu(3+)-Gd(3+)-containing metallopolymer Poly(2-co-NVK-co-4), which also showed tunable purplish-blue to white to yellow-green photoluminescence.