Multi‐resonant thermally activated delayed fluorescence (MR‐TADF) emitters have attracted strong interest for organic electroluminescent devices due to their high photoluminescence quantum yield (ΦPL) and narrowband emission. These properties are also crucial for high‐performance biological probes, especially red emitters. Orange and red MR‐TADF emitters, PhDPA‐DiKTa and MeODPA‐DiKTa, are designed by decorating the DiKTa core with di([1,1′‐biphenyl]‐4‐yl)amine and bis(4‐methoxyphenyl)amine, respectively. As 5 wt.% doped films in 1,3‐di(9H‐carbazol‐9‐yl)benzene (mCP), PhDPA‐DiKTa emits at λPL of 617 nm, while MeODPA‐DiKTa emits at λPL of 655 nm. Both show delayed fluorescence, with delayed lifetimes, τd, of 658.4 and 249.2 µs, respectively. Water‐dispersible glassy organic dots (g‐Odots) based on these materials are prepared by encapsulating them and mCP host into an amphiphilic DSPE‐PEG2k polymer. Both families of g‐Odots showed a deeper red emission and enhanced ΦPL compared to the corresponding 5 wt.% doped films in mCP (λPL = 618 nm, ΦPL = 77% for PhDPA‐DiKTa g‐Odots, λPL = 663 nm, ΦPL = 38% for MeODPA‐DiKTa g‐Odots). The TADF character of the emitters is conserved in the g‐ODots, with τd of 203.9 µs for PhDPA‐DiKTa g‐Odots and 131.6 µs for MeODPA‐DiKTa g‐Odots. These MR‐TADF g‐Odots are successfully demonstrated as biological imaging probes of HeLa cells.