To achieve an ultimate wide color gamut for ultrahigh-definition displays, there is great demand for the development of organic light-emitting diodes (OLEDs) enabling monochromatic, ultrapure blue electroluminescence (EL). Herein, high-efficiency and ultrapure blue OLEDs based on polycyclo-heteraborin multi-resonance thermally activated delayed fluorescence (MR-TADF) materials, BOBO-Z, BOBS-Z, and BSBS-Z, are reported. The key to the design of the present luminophores is the exquisite combination and interplay of multiple boron, nitrogen, oxygen, and sulfur heteroatoms embedded in a fused polycyclic π-system. Comprehensive photophysical and computational investigations of this family of MR-TADF materials reveal that the systematic implementation of chalcogen (oxygen and sulfur) atoms can finely modulate the emission color while maintaining a narrow bandwidth, as well as the spin-flipping rates between the excited singlet and triplet states. Consequently, OLEDs based on BOBO-Z, BOBS-Z, and BSBS-Z demonstrate narrowband and ultrapure blue EL emission, with peaks at 445-463nm and full width at half maxima of 18-23nm, leading to Commission Internationale de l'Éclairage-y coordinates in the range of 0.04-0.08. Particularly, for OLEDs incorporating sulfur-doped BOBS-Z and BSBS-Z, notably high maximum external EL quantum efficiencies of 26.9% and 26.8%, respectively, and small efficiency roll-offs are achieved concurrently.