A set of laser apparatus was used to study induction period and primary nucleation of lithium carbonate in reactive crystallization. The results show that induction period increases with the decrease of supersaturation degree and temperature. Magnetic field has nearly no impact on it, while the use of ultrasound reduces it obviously. The impacts of some impurities and additives on primary nucleation were investigated. It is found that the presence of Na2SO4, NH4Cl, (NH4)2SO4 and EDTA disodium prolongs induction period, whereas KCl, NaCl, NaBr and CH4N2O can decrease it. Many important parameters of primary nucleation are also obtained, as temperature goes up from 283 to 313 K, interracial tension decreases from 44.8 to 41.5 mJ/m2, contact angle varies from 82.9° to 88.7°, nucleation order is between 5.0 and 5.4, surface entropy factors are all above 5, suggesting that the growth mechanism is a spiral growth. Besides, both the homogeneous and heterogeneous primary nucleations were monitored with on-line focused beam reflectance measurement.