The results of the first experiments with a spin-echo small-angle neutron scattering (SESANS) device built at the VVR-M reactor at the St. Petersburg Institute of Nuclear Physics (Gatchina) are presented. SESANS utilizes the possibilities of the spin-echo method for determining the structural characteristics of materials in real space with on the 10–104-nm length scale. Validation measurements are conducted using SiO2 colloidal particles. Samples of SiO2 spheres with a diameter determined through scanning electron microscopy and synchrotron-radiation ultra-small-angle scattering are used for calibration of the device. Approximation of the data obtained with the SESANS device was conducted using the autocorrelation function for dilute monodisperse spheres. The sizes of the spheres determined via SESANS are in agreement with those determined by other methods within the experimental error.