Chuck Smith emphasizes the sin of prayerlessness, highlighting how it is a reproach to God who invites us to fellowship with Him. He explains that neglecting prayer hinders God's work and reflects disobedience to His command. Smith urges believers to pray for one another, especially during times of failure, and identifies common hindrances to prayer such as lack of time and distractions. He encourages practical solutions to overcome these barriers, advocating for intentionality in prayer life.