The confinement of liquid crystals (LCs) in spherical microdroplets results in exotic internal configurations and topological defects in response to physical and chemical stimuli. Recent exploration into the placement of colloids on the surface of LC microdroplets has led to the design of a new class of functional materials with patterned surface properties. It is established that the placement of a colloid on a LC droplet surface can pin the topological defect at the interface, thereby restricting changes in the LC configuration. Herein, we build upon the handful of reports published to provide a fundamental understanding of the colloid positioning in response to external stimuli. Using polystyrene (PS) colloids, we explored the dynamics of particle self-assembly in response to an interfacial enzymatic breakdown of poly-L-lysine by trypsin. We found that for a significant population of droplets, the positioning of the colloid is unaffected by the changes in the internal ordering of LC. Inspired by the new observations, we delved deeper to understand the role of interfacial stabilizers in modulating the preferential alignment of LC and the placement of colloidal microparticles. We also demonstrated that for a certain population of droplets, the positioning of the colloids remains unperturbed in response to multistep reversible adsorption of interfacial amphiphiles. Our findings reveal interesting possibilities of correlating the stimuli-responsive switching of internal configurations of LC with colloid placement on the particle-decorated LC droplets.