A facile solution-chemical method has been developed to be capable of encapsulating a multiwalled carbon nanotube (MWCNT) with ZnS nanocrystals without using any bridging species. The thickness of the ZnS shell can be tuned easily by controlling the experimental conditions. The optical properties of the MWCNT/ZnS heterostructures were investigated using UV-vis absorption and photoluminescence spectroscopy. The optical absorption spectrum indicates that the band gap of ZnS nanocrystallites is 4.2 eV. On the basis of the photoluminescence spectrum, charge transfer is thought to proceed from ZnS nanocrystals to the nanotube in the ZnS-carbon nanotube system. These special heterostructures are very easily encapsulated within a uniform silica layer by a modified-Stöber process and still show better stability even after heat treatment at 400 °C, which makes them appealing for practical applications in biochemistry and biodiagnostics.