Morphology and NMR self-diffusion of two miktoarm star copolymers differing in fraction of poly(n-butyl acrylate) and poly(ethylene oxide) (PBA and PEO) arms were under investigation. Structural characteristics of copolymers was obtained on the basis of Small Angle X-Ray Scattering (SAXS) investigations. The phase separated nanoscale morphology of the miktoarm star copolymer with a high fraction of PEO arms was confirmed by Scanning Probe Microscopy (SPM) studies. The modified Avrami approach was used to obtain the information on the non-isothermal crystallization kinetics of the studied systems. It was observed that the crystallization in the system with a higher content of PBA, occurring at higher undercooling, was characterized by a higher crystallization rate. It was also found that increase in PBA arms fraction leads to the reduction in the size of PEO domains. The activation energy of the crystallization process, estimated with Kissinger's method, is lower for miktoarm star copolymer with higher PBA content, which results from facilitation of the transport of PEO chains in the direction of the growing crystal due to the presence of mobile PBA arms. The self-diffusion studies of miktoarm star copolymers melts, carried out with the Pulsed-Gradient STimulated-Echo (PGSTE) Nuclear Magnetic Resonance (NMR) technique, reveals the existence of at least two types of diffusion mechanisms in these systems.