The set of end‐to‐end vectors (hereafter called the discrete‐state distribution) for a model polymer chain ofnbonds has been generated for a three rotational state model on the B‐5000 computer. Equally probablegauche‐right,trans, andgauche‐left states are assumed. The discrete‐state distribution is determined for a polydimethylsiloxane chain withn=6, 8, 10 and a polyethylene chain withn=6, 8. For a polyethylene chain of six links the calculated distribution is shown to differ substantially from a normalized Gaussian. For each case, a function is obtained for the discrete‐state distribution through the Gram‐Charlier technique of expanding an unknown functionf(x) in terms of a Gaussian function. The Gram‐Charlier expansion is shown to give a reasonable fit to the discrete‐state distribution. The distributionf(x) is shown to more accurately predict the equilibrium formation of octamethylcyclotetrasiloxane in a dimethylsiloxane polymer than does the Gaussian distribution. The problem of excluded volume is not considered for the short chains treated here.