Teaching approaches for the 21st century learners (the netizens) have redefined the roles of teachers in modern classrooms. Therefore, the paper explored the extent of teachers’ preparation and appropriate learning environment for effective teaching of requisite skills to 21st century learners. A descriptive survey was adopted. The study was carried out in two education zones in Anambra State, Nigeria. Four research questions and four hypotheses guided the study. Geographical location was taken into consideration for the purposive selection of 10 schools while simple random sampling based on balloting was used for the selection of 2 education zones. Teacher’s ranks were also considered to select 564 while individual consents were used to select 770 learners. The instruments for data collection were 30-item questionnaire for teachers and 10-item for learners. The instruments were validated and reliability coefficients were computed to be 0.84 for teachers and 0.80 for students. Data were analyzed using means, standard deviation and rank order for research questions and t-test for hypotheses at 0.05 level of significance. Results showed that teachers’ preparation was at a low level and the learning environment was not suitable for 21st century learners. Recommendations were made among which were that secondary school teachers should be trained in line with the 21st century skills and the learning environment should be technologically equipped for challenges of 21st century teaching and learning.