To clarify the effect of W contents on the shape memory effect (SME) in the Co-Al alloys and its influencing mechanism, the SME, martensitic transformation, and deformation behavior were studied in the Co-7Al-xW (x = 0, 4, 6, 9 wt pct) alloys. The results showed that the additions of W all deteriorated the SME in Co-7Al alloy when deformed at room temperature. However, when deformed in liquid nitrogen, the SME in Co-7Al alloy could be remarkably improved from 43 to 78 pct after the addition of 4 pct W, above which the SME decreased rapidly with the increase of W content although the yield strength of the parent phase rose due to the solution strengthening of W. The deterioration in SME induced by the excessive addition of W could be ascribed to its resulting significant drop of the start temperature of martensitic transformation.