In the mixed-valence manganites, a near-infrared laser typically melts the orbital and spin order simultaneously, corresponding to the photoinduced d¹d⁰ → d⁰d¹ excitations in the Mott-Hubbard bands of manganese. Here, we use ultrafast methods—both femtosecond resonant x-ray diffraction and optical reflectivity—to demonstrate that the orbital response in the layered manganite Nd_1−xSr_1+xMnO₄ (x = 2/3) does not follow this scheme. At the photoexcitation saturation fluence, the orbital order is only diminished by a few percent in the transient state. Instead of the typical d¹d⁰ → d⁰d¹ transition, a near-infrared pump in this compound promotes a fundamentally distinct mechanism of charge transfer, the d⁰ → d¹L, where L denotes a hole in the oxygen band. This finding may pave a different avenue for selectively manipulating specific types of order in complex materials of this class.