This study is devoted to synthesis and characterization of uranium dioxide microspheres (Ø < 100 µm) and pellets by application of powder-free process called the Complex Sol-Gel Process. The precursors of prepared sols were ascorbic acid solution with dissolved a freshly precipitated ammonium diuranate. The microspheres of uranyl-ascorbate gel were obtained using the ICHTJ Process. The pellets were formed by pressing and sintering of uranium dioxide powder. Studies allowed determining an optimal heat treatment of calcination, reduction and sintering processes at temperatures of 700°C, 900°C and 1300°C, respectively. The main parameters which play a key role in the process of synthesis method and features of the pellets and microspheres of uranium dioxide are described in this article.