The product rotational alignment [P-2((J) over cap'.(k) over cap)] = -0.35 +/- 0.04, -0.15 +/- 0.02 for CaCl(B), CaCl(A) are obtained from Ca + NOCl chemiluminescent reactions, respectively. The experiments are carried out under single collision conditions in a beam-gas apparatus. Quasi-classical trajectory (QCT) calculations for Ca + NOCl reaction have been carried out. The calculated results agree well with the experimental ones. The strong product alignments for the reactions are attributed to attractive potential surfaces. It is plausible that the difference of the rotational alignment between the A(2) Pi and B-2 Sigma states of the products is due to their different potential energy surfaces (PESs).