A rapid flow-through, highly sensitive microfluidic photoionization detector (PID) which is micro-fabricated directly onto a substrate, such as a conductive silicon wafer, is provided. The microfluidic PID has an ionization chamber volume of less than 9 μL. The microfluidic PID may have a flow through design with a microfluidic channel defines a serpentine pattern on the substrate. The flow through design of the microfluidic PID results in negligible dead volume, thus allowing a shortened response time over existing commercially available designs. Such microfluidic PIDs are particularly useful with gas chromatography (GC), including microGC and multi-dimensional microGC systems. Methods for calibrating PIDs are also provided.