A generalized scheme for phase-conjugate resonant 2n-wave mixing, which has a high efficiency and is easy for phase matching, is proposed. As a new type of coherent laser spectroscopy this approach can be employed for studying highly excited atomic states or states with a high angular momentum. To demonstrate its feasibility we have studied the doubly excited autoionizing Rydberg states of Ba by phase-conjugate six-wave mixing, and have furthermore achieved eight-wave mixing in Na. This method may find wide application in related areas such as coherent transient spectroscopy, Autler-Townes spectroscopy and electromagnetically induced transparency. In particular, it may provide new insights into the nature of highly excited states.