The oil-absorption behavior of native maize starch (NMS) during frying was investigated in the presence or absence of pullulan (PUL) using a LF-NMR method. The morphology, long-range order, short-range order, and thermal properties of fried NMS-PUL mixtures were further evaluated using SEM, XRD, ATR-FTIR, and DSC, respectively. Pullulan addition significantly reduced the oil content of the fried starch samples: 0.395, 0.310, 0.274, and 0.257 g/g in NMS with addition of 0, 1, 3, and 5% PUL, respectively (p < 0.05). SEM analysis showed that the intact granular morphology of the starch granules was preserved upon addition of pullulan. The XRD, FTIR, and DSC results showed that pullulan protected both the short-range double helices and long-range crystalline structure of the granules during frying. As a result, fried NMS-PUL mixtures were denser than fried NMS, thus inhibiting oil absorption during frying. These results may have important implications for creating healthier reduced-fat fried food products.