A CuSr2(Y, Ca) Cu2Oy superconductor was obtained under atmospheric pressure using a sol-gel method. A material including this superconductive phase showed diamagnetic behaviour from 45 K and a drastic decrease of resistance from 51 K. It was found from X-ray diffraction and high-resolution transmission electron microscopy studies that the superconductive crystal has a tetragonal symmetry of a = 0.382 nm and c = 1.129 nm, and no superstructural ordering was found. However, we cannot completely rule out the possibility of carbon contamination on copper sites. It has been demonstrated that the sol-gel method is a promising route to synthesize high pressure phases of cuprate superconductors.