Photo-origami uses the dynamic control of the molecular architecture of a polymer by a combination of mechanical and non-contact optical stimuli to design and program spatially and temporally variable mechanical and optical fields into a material. The fields are essentially actuators, embedded in the material at molecular resolution, designed to enable controllable, sequenced, macroscopic bending and folding to create three-dimensional material structures. Here, we demonstrate, through a combination of theory, simulation-based design, synthesis, and experiment, the operative phenomena and capabilities of photo-origami that highlight its potential as a powerful, and potentially manufacturable, approach to create three-dimensional material structures.