Laser cooling and precision laser spectroscopy experiments of relativistic highly charged ions are being prepared at the heavy‐ion experimental cooler storage ring (CSRe). Optical detection of fluorescence photons, emitted from the laser‐excited ions, is extremely important for both powerful methods. In this paper, we briefly report on the current status of the existing optical detectors and also on their performance during laser cooling of relativistic Li‐like 16O5+ ion beams at the CSRe. In addition, we introduce the designs for our new optical detection systems, which have much higher photon detection efficiencies and can cover a much broader wavelength range. These detector systems will be used for the upcoming laser spectroscopy experiment of Li‐like 16O5+ ions, as well as for future laser spectroscopy experiments with other highly charged ions.