We have used wet chemical methods to fabricate colloidal CdSe/CdSm/ZnSen core/intermediate/shell (C/I/S) nanocrystals (NCs), where m = 1 and 2 and n = 1–4 are the number of monolayers. The growth was monitored by using Raman and UV–vis spectroscopy, which demonstrated the formation of correct CdSe/CdSm/ZnSen C/I/S NCs. X-ray diffraction studies proved single-phase NCs crystallized in the zincblende-type structure. Photoluminescence (PL) studies have indicated that after photoexcitation C/I/S NCs generate simultaneously type-I and type-II emissions, namely E I and E II , associated with CdSe/CdSm and CdSm/ZnSen structures, respectively. For a specific value of m = 2, we have found the redshift of both E I and E II emissions when n is increased from 1 to 4. The PL studies versus the laser-excitation power (P ex ) up to about four orders of magnitude allow us to identify the origin of two emissions. A large blueshift of the E II peak is ascribed to the band bending effect resulting from the spatially separated photoexcited carriers in type-II NCs. It appears that the dependence of the E II peak on the cube root of P ex (P ex 1/3 ) is linear while that of the E I peak on P ex 1/3 is almost constant. In this work, we also point out that the emission intensity (I) of E I and E II can be tuned by changing the values of n and P ex , where I obeys a power law I∝P ex k , with k = 0.7–1.0 dependent on the emission type. The nature of these phenomena is discussed in comparison with previous studies on C/S and C/I/S nanoheterostructures.