Starch particles (SPs) were extracted from underutilized wild yam (Dioscorea remotiflora) tubers using two methods: (1) acid hydrolysis (AH) alone and (2) acid hydrolysis assisted by ultrasound (AH-US). The SPs were chemically modified through esterification (using acetic anhydride [AA] and lauroyl chloride [LC]) and crosslinking (with citric acid [CA] and sodium hexametaphosphate [SHMP]). They were subsequently characterized by their yield, amylose content, and structural and physical properties. The yield of particles was 17.5–19.7%, and the residual amylose content was 2.8–3.2%. Particle sizes ranged from 0.46 to 0.55 µm, which exhibited mono-modal and bi-modal distributions for AH and AH-US treatments, respectively. Following chemical modification, yield notably increased, especially with substitution by LC (33.6–36.5%) and CA (32.6–38.7%). Modified SPs exhibited bi-modal particle distributions with micro- and nanoparticles and variable peak intensities depending on the chemical compound used. Unmodified SPs displayed irregular morphologies, showing disruptions (AH) or aggregation (AH-US). Chemical substitutions altered morphologies, leading to amorphous surfaces (CA: AH), clustering (LC), or fragmentation into smaller particles (SHMP) under AH-US treatment. FT-IR analysis indicated a decrease in hydroxyl groups’ peak area (A(-OH)), confirming the substitution of these groups in the starch structure. Crosslinking with CA resulted in the highest degree of substitution (AH: 0.43; AH-US: 0.44) and melting enthalpy (ΔH_f: 343.0 J/g for AH-US), revealing stronger interactions between SPs from both methods. These findings demonstrate that the extraction treatment of D. remotiflora SPs and the type of chemical modifier significantly influence the properties of SPs, underscoring their potential applications as natural biocarriers.