Conventional Langmuir probe cannot be used in most reactive plasmas for materials processing, owing to the insulating layers that are deposited on the probe surface. To address this issue, a novel variety of microwave probes has been recently developed for the purpose of monitoring local electron density, which is a key parameter for plasma control. The probe diagnostic must be stable, compact, easy, exhibiting negligible disturbance to a plasma and materials processing. This article presents a review of the diagnostic principle, characteristics and applications of representative probes such as the plasma oscillation probe, surface wave probe (plasma absorption probe), multi-pole resonance probe, hairpin probe and curling probe. The merits and demerits of each probe are presented from a reactive plasma diagnostic point of view. Innovations in the applications of microwave probes to optical emission spectrometry and the monitoring of wall deposits are also presented.