To investigate the relationship between structures and adsorption properties, four different morphologies of chitosan, with hydrogel (CSH), aerogel (CSA), powder (CSP), and electrospinning nanofiber (CSEN) characteristics, were employed as adsorbents for the removal of Acid Red 27. The structures and morphologies of the four chitosan adsorbents were characterized with SEM, XRD, ATR-FTIR, and BET methods. The adsorption behaviors and mechanisms of the four chitosan adsorbents were comparatively studied. All adsorption behaviors exhibited a good fit with the pseudo-second-order kinetic model (R² > 0.99) and Langmuir isotherm model (R² > 0.99). Comparing the adsorption rates and the maximum adsorption capacities, the order was CSH > CSA > CSP > CSEN. The maximum adsorption capacities of CSH, CSA, CSP, and CSEN were 2732.2 (4.523), 676.7 (1.119), 534.8 (0.885), and 215.5 (0.357) mg/g (mmol/g) at 20 °C, respectively. The crystallinities of CSH, CSA, CSP, and CSEN were calculated as 0.41%, 6.97%, 8.76%, and 39.77%, respectively. The crystallinity of the four chitosan adsorbents was the main factor impacting the adsorption rates and adsorption capacities, compared with the specific surface area. With the decrease in crystallinity, the adsorption rates and capacities of the four chitosan adsorbents increased gradually under the same experimental conditions. CSH with a low crystallinity and large specific surface area resulted in the highest adsorption rate and capacity.