An experimental study is reported of supersonic jet surface flow structure visualization and wall shear stress field measurement issuing from a rectangular nozzle with aft-deck. The near-field surface flow structures evolution from over-expansion to under-expansion with the increase of nozzle pressure ratio (NPR) are successfully captured by surface oil flow visualization and shear sensitive liquid crystal coating (SSLCC) technique. The quantitative measurement result of shear stress vector field obtained by SSLCC shows that shear stress directions change significantly across the shock wave and expansion fans, while the magnitudes of shear stress have no obvious changes. Surface streamlines calculated by SSLCC image keep great consistency with the streamlines visualized using oil flow technique, which demonstrates the accuracy and potential application of SSLCC in supersonic jet surface flow visualization.