In this paper, we introduce a new and simple method of patterning polydimethylsiloxane (PDMS) directly using benzophenone as a photoinitiator. The photodefinable PDMS mixture (photoPDMS) is positive-acting and only sensitive to light below 365 nm, permitting processing under normal ambient light. Features of the order of 100 microm, which are sufficiently small for most microfluidic applications, were successfully fabricated using this novel process. A parametric study of process parameters was performed to optimize the fabrication. As a demonstration, microfluidic channels of varying dimensions were successfully fabricated using this process and experimentally characterized using fluorescence microscopy. To further demonstrate photoPDMS potential, thin (<30 microm) free-standing films with through patterns were fabricated and successfully used as shadow masks. The photoPDMS process completely eliminates the need for a master, permits processing under normal ambient light conditions, and makes fabrication fast and simple. This process for rapid prototyping of low-cost, disposable LOCs can be accomplished without cleanroom facilities and thus can be employed for a wide range of applications.