We perform a search of double beta decay of 136Xe to the excited state, \( {0}_1^{+} \) , of 136Ba (2νββ- \( {0}_1^{+} \) ), using the dual-phase xenon detector of PandaX-4T with the first 94.9-day commissioning data. The multi-site events are reconstructed up to the MeV energy scale, which helps to improve the background model significantly. The background contribution from the stainless steel platform outside PandaX-4T cryostat is evaluated for the first time. No significant evidence for 2νββ- \( {0}_1^{+} \) is observed, resulting in a lower limit on half-life of 7.5 × 1022 yr at the 90% confidence level. This is the first experimental limit on such a rare decay in a natural xenon-based detector.
