Fully sustainable shape memory polymers (SMPs) derived from ethyl cellulose (EC, derived from cellulose), tetrahydrofurfuryl methacrylate (THFMA, derived from furfural), and lauryl methacrylate (LMA, derived from fatty acids) were prepared via grafting from atom transfer radical polymer (ATRP). The grafting from ATRP strategy allows to fabricate SMPs with EC as a backbone, and LMA and THFMA copolymer as a side chain. By utilizing the one-pot and sequential monomer addition approach, two types of SMPs with random/semi-block side chain architectures were obtained, respectively. Random/semi-block side chain architecture of SMPs was confirmed by DSC, DMA, SAXS, and TEM. The presence of microphase separation in the SMPs with semi-block side chain architecture provided two distinct thermal transitions, which was needed for triple-shape memory behavior. Shape memory study showed that SMPs with semi-block side chain architecture exhibited excellent triple-shape memory property, and also had higher shape recovery speed and shape recovery ratio than those with random side chain architecture. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1711-1720