We describe the realization of integrated optical chromatography, in conjunction with on-chip fluorescence excitation, in a monolithically fabricated poly-dimethylsiloxane (PDMS) microfluidic chip. The unique endlessly-single-mode guiding property of the Photonic Crystal Fiber (PCF) facilitates simultaneous on-chip delivery of beams to perform optical sorting in conjunction with fluorescence excitation. We use soft lithography to define the chip and insert the specially capped PCF into it through a predefined fiber channel that is intrinsically aligned with the sorting channel. We compare the performance of the system to a standard ray optics model and use the system to demonstrate both size-driven and refractive index-driven separations of colloids. Finally we demonstrate a new technique of enhanced optofluidic separation of biological particles, by sorting of human kidney embryonic cells (HEK-293), internally tagged with fluorescing microspheres through phagocytocis, from those without microspheres and the separation purity is monitored using fluorescence imaging.