A highly sensitive electron energy analyzer which utilizes a "magnetic bottle" combined with a retarding electrostatic field has been developed for Penning ionization electron spectroscopy. A beam of metastable rare-gas atoms is crossed with a continuous supersonic sample beam in the source region of the analyzer. The emitted electrons are collected by an inhomogeneous magnetic field (the magnetic bottle effect) with a high efficiency of nearly 4 π solid angle, which is more than 103 times higher than that of a conventional hemispherical analyzer. The kinetic energy of electrons is analyzed by scanning the retarding field in a flight tube of the analyzer in the presence of a weak magnetic field. The velocity of the metastable atoms can also be resolved by a time-of-flight method in the present instrument. Examples of Penning ionization electron energy spectra as a function of collision energy are presented for Ar and N2 with metastable He*(2 3S) atoms. This instrument has opened the possibility for extensive studies of Penning ionization electron spectroscopy for low-density species, such as clusters, ions, electronically excited species, unstable or transient species, and large molecules with low volatility.