Complexation can be utilized to modify starch properties. In this study, tapioca starch–methyl myristate complexes were prepared by mixing tapioca starch and methyl myristate in water at 90°C. The methyl myristate amount was varied at 1–10% (w/w) to study its effects on the complexes’ physicochemical properties, which were characterized using spectroscopic (UV–Vis, ATR‐FTIR, Raman, UV‐DRS), thermal (DSC, TGA), crystallinity (XRD), particle size (PSA), and microscopic (SEM) analyses. The complexes were stable crystalline materials, as iodine could not replace complexed methyl myristate. In water, these complexes aggregated to form two different sizes of 29.5–162.7 nm (23–58% population) and 711.2–7086.7 nm (42–77% population), which melted at 90–95°C. Solid complexes formed porous morphologies, which started degrading at 260.3–263.4°C, indicating high thermal stability. An in vitro digestibility study using α‐amylase showed that the higher the methyl myristate amount was, the slower the starch degradation. At 120 min digestion time, the complexes produced 11–16% lower reducing sugar than native starch. This showed that starch complexation with methyl myristate complexes could produce starch materials with slower digestibility. For the kinetic analysis, the Weibull model fitted better than the exponential model for analyzing the digestion kinetics of starch–methyl myristate complexes by the α‐amylase enzyme.This article is protected by copyright. All rights reserved