Dual stimuli responsive polyelectrolyte nanoparticles have been developed for chemo-photothermal synergistic therapy of colon cancer cells. This novel system is formed by layer by layer (LbL) assembly, which is composed of aminated nanodextran (AND) and carboxylated nanocellulose (CNC) deposited on the surface of chemically modified graphene oxide (MGO). The alternate layers of cationic AND and anionic CNC interact with MGO through electrostatic interaction and forms MGO-AND/CNC nanocomposite. The MGO-AND/CNC exploited for the encapsulation of anticancer drug curcumin (CUR) by π-π stacking and hydrogen bonding interactions. Various concentrations of MGO and AND/CNC were examined and the optimal hydrodynamic size of the particle was found to have 158.0 nm, zeta potential of -45.9 ± 6.9 mV and encapsulation efficiency of 86.4 ± 4.7%. The resulting nanocomposite was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and zeta potential measurements. Drug release assay indicates that the LbL MGO-AND/CNC releases much faster in an acidic environment than intestinal pH. A cytotoxicity assay was conducted to prove the efficacy of drug loaded MGO-AND/CNC to destroy HCT116 cells in response to near-infrared (NIR) laser emission. Study results suggest the novel dual-sensitive nanoparticles allow intracellular curcumin delivery and respond to either acidic environments or NIR excitation.