The successful preparation of starch-based Pickering emulsions typically relies on the use of high-viscosity or high-boiling-point oil solvents. However, these solvents present challenges in removal and limit the applicability of the emulsions. This study aims to investigate the feasibility and effectiveness of employing small-molecule solvents as alternatives for the oil phase. Specifically, quinoa starch granules are used as the emulsifying agent with a systematic exploration of various small molecules from different solvent categories. This research contributes by identifying the impact of solvent-particle interactions on the feasibility of emulsion formation—an aspect critical but often overlooked in previous discussions on solvent influence on emulsion quality, essential for guiding solvent selection. Furthermore, to address potential challenges associated with maintaining emulsion stability when using low-viscosity oils, a strategy based on exploiting depletion attraction is proposed and demonstrated, leveraging bovine serum albumin as depletants.